Fibrous structures comprising particles and methods for making same

ABSTRACT

Fibrous structures containing one or more particles, and methods for making same are provided.

FIELD OF THE INVENTION

The present invention relates to fibrous structures, more particularlyto fibrous structures comprising one or more particles, and methods formaking same.

BACKGROUND OF THE INVENTION

Fibrous structures comprising particles are known in the art. Forexample, as shown in FIG. 1, a water-insoluble polypropylenefilament-containing fibrous structure 10 comprising polypropylenefilaments 12 and pulp fibers 14 is known in the art. In addition, asshown in FIG. 2, a water-insoluble starch filament-containing fibrousstructure 16 comprising crosslinked, water-insoluble starch filaments 18and pulp fibers 14 is known in the art. Further, as shown in FIG. 3, awater-insoluble starch filament-containing fibrous structure 16comprising crosslinked, water-insoluble starch filaments 18 andwater-insoluble particles 20 such as surfactant-coated polyolefinparticles, surfactant-coated polyester particles and/or an aluminumsilicate particles is also known. Further yet, FIG. 4 illustrates afibrous structure 22 comprising water-insoluble thermoplastic polymerfilaments 24 and water-insoluble organic and/or mineral particles 26.

However, consumers still desire new and improved fibrous structurescomprising fibrous elements, such as filaments, for examplewater-soluble filaments and/or fibrous elements that comprise one ormore active agents, and particles, such as active agent-containingparticles, for example water-soluble, active agent-containing particlesand/or water-insoluble particles.

The problem faced by formulators of fibrous structures is that consumersof fibrous structures desire more and different performance and/orproperties from fibrous structures, especially fibrous structures thatcomprise particles.

In light of the foregoing, it is clear that there is a need for newfibrous structures that meet consumers' expectations in variousapplications.

SUMMARY OF THE INVENTION

The present invention fulfills the need described above by providingnovel fibrous structures comprising particles.

In one example of the present invention, a fibrous structure comprisinga plurality of fibrous elements and one or more water-soluble, activeagent-containing particles, is provided.

In another example of the present invention, a fibrous structurecomprising a plurality of fibrous elements comprising one or more activeagents that are releasable from the fibrous element when exposed toconditions of intended use and one or more active agent-containingparticles, is provided.

In still another example of the present invention, a fibrous structurecomprising a plurality of fibrous elements comprising one or more activeagents that are releasable from the fibrous element when exposed toconditions of intended use and one or more water-soluble, activeagent-containing particles, is provided.

In yet another example of the present invention, a fibrous structurecomprising a plurality of water-soluble fibrous elements and one or moreactive agent-containing particles, is provided.

In even still yet another example of the present invention, a fibrousstructure comprising a plurality of fibrous elements comprising one ormore active agents that are releasable from the fibrous element whenexposed to conditions of intended use and one or more particles, isprovided.

In even another example of the present invention, a method for making afibrous structure, the method comprising the steps of:

a. providing a fibrous element-forming composition comprising one ormore filament-forming materials;

b. spinning the fibrous element-forming composition into one or morefibrous elements;

c. providing one or more active agent-containing particles; and

d. associating the one or more active agent-containing particles withthe one or more fibrous elements to form a fibrous structure, isprovided.

Accordingly, the present invention provides fibrous structurescomprising particles and methods for making such fibrous structures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a prior art water-insolublepolypropylene filament-containing fibrous structure comprising pulpfibers;

FIG. 2 is a schematic representation of a prior art crosslinked,water-insoluble starch filament-containing fibrous structure comprisingpulp fibers;

FIG. 3 is a schematic representation of a prior art crosslinked,water-insoluble starch filament-containing fibrous structure comprisingwater-insoluble particles;

FIG. 4 is a schematic representation of a prior art water-insolublethermoplastic polymer filament-containing fibrous structure comprisingwater-insoluble organic and/or mineral particles;

FIG. 5 is a scanning electron microscope photograph of a cross-sectionalview of an example of a fibrous structure according to the presentinvention;

FIG. 6 is a schematic representation of a cross-sectional view ofanother example of a fibrous structure according to the presentinvention;

FIG. 7 is a schematic representation of a cross-sectional view ofanother example of a fibrous structure according to the presentinvention;

FIG. 8 is a scanning electron microscope photograph of a cross-sectionalview of another example of a fibrous structure according to the presentinvention;

FIG. 9 is a schematic representation of an example of a process formaking fibrous elements of the present invention;

FIG. 10 is a schematic representation of an example of a die with amagnified view used in the process of FIG. 9;

FIG. 11 is a schematic representation of an example of a process formaking a fibrous structure according to the present invention;

FIG. 12 is a schematic representation of another example of a processfor making a fibrous structure according to the present invention;

FIG. 13 is a schematic representation of another example of a processfor making a fibrous structure according to the present invention;

FIG. 14 is a representative image of an example of a patterned beltuseful in the present invention;

FIG. 15 is a schematic representation of an example of a setup ofequipment used in measuring dissolution according to the presentinvention;

FIG. 16 is a schematic representation of FIG. 15 with during theoperation of the dissolution test; and

FIG. 17 is a schematic representation of a top view of FIG. 16.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“Fibrous structure” as used herein means a structure that comprises oneor more fibrous elements and one or more particles. In one example, afibrous structure according to the present invention means anassociation of fibrous elements and particles that together form astructure, such as a unitary structure, capable of performing afunction.

The fibrous structures of the present invention may be homogeneous ormay be layered. If layered, the fibrous structures may comprise at leasttwo and/or at least three and/or at least four and/or at least fivelayers, for example one or more fibrous element layers, one or moreparticle layers and/or one or more fibrous element/particle mixturelayer.

In one example, the fibrous structure is a multi-ply fibrous structurethat exhibits a basis weight of less than 5000 g/m² as measuredaccording to the Basis Weight Test Method described herein.

In one example, the fibrous structure of the present invention is a“unitary fibrous structure.”

“Unitary fibrous structure” as used herein is an arrangement comprisinga one or more particles and a plurality of two or more and/or three ormore fibrous elements that are inter-entangled or otherwise associatedwith one another to form a fibrous structure. A unitary fibrousstructure of the present invention may be one or more plies within amulti-ply fibrous structure. In one example, a unitary fibrous structureof the present invention may comprise three or more different fibrouselements. In another example, a unitary fibrous structure of the presentinvention may comprise two different fibrous elements, for example aco-formed fibrous structure, upon which a different fibrous element isdeposited to form a fibrous structure comprising three or more differentfibrous elements.

“Fibrous element” as used herein means an elongate particulate having alength greatly exceeding its average diameter, i.e. a length to averagediameter ratio of at least about 10. A fibrous element may be a filamentor a fiber. In one example, the fibrous element is a single fibrouselement rather than a yarn comprising a plurality of fibrous elements.

The fibrous elements of the present invention may be spun from afilament-forming compositions also referred to as fibrouselement-forming compositions via suitable spinning process operations,such as meltblowing, spunbonding, electro-spinning, and/or rotaryspinning.

The fibrous elements of the present invention may be monocomponentand/or multicomponent. For example, the fibrous elements may comprisebicomponent fibers and/or filaments. The bicomponent fibers and/orfilaments may be in any form, such as side-by-side, core and sheath,islands-in-the-sea and the like.

“Filament” as used herein means an elongate particulate as describedabove that exhibits a length of greater than or equal to 5.08 cm (2 in.)and/or greater than or equal to 7.62 cm (3 in.) and/or greater than orequal to 10.16 cm (4 in.) and/or greater than or equal to 15.24 cm (6in.).

Filaments are typically considered continuous or substantiallycontinuous in nature. Filaments are relatively longer than fibers.Non-limiting examples of filaments include meltblown and/or spunbondfilaments. Non-limiting examples of polymers that can be spun intofilaments include natural polymers, such as starch, starch derivatives,cellulose, such as rayon and/or lyocell, and cellulose derivatives,hemicellulose, hemicellulose derivatives, and synthetic polymersincluding, but not limited to thermoplastic polymer filaments, such aspolyesters, nylons, polyolefins such as polypropylene filaments,polyethylene filaments, and biodegradable thermoplastic fibers such aspolylactic acid filaments, polyhydroxyalkanoate filaments,polyesteramide filaments and polycaprolactone filaments.

“Fiber” as used herein means an elongate particulate as described abovethat exhibits a length of less than 5.08 cm (2 in.) and/or less than3.81 cm (1.5 in.) and/or less than 2.54 cm (1 in.).

Fibers are typically considered discontinuous in nature. Non-limitingexamples of fibers include staple fibers produced by spinning a filamentor filament tow of the present invention and then cutting the filamentor filament tow into segments of less than 5.08 cm (2 in.) thusproducing fibers.

In one example, one or more fibers may be formed from a filament of thepresent invention, such as when the filaments are cut to shorter lengths(such as less than 5.08 cm in length). Thus, in one example, the presentinvention also includes a fiber made from a filament of the presentinvention, such as a fiber comprising one or more filament-formingmaterials and one or more additives, such as active agents. Therefore,references to filament and/or filaments of the present invention hereinalso include fibers made from such filament and/or filaments unlessotherwise noted. Fibers are typically considered discontinuous in naturerelative to filaments, which are considered continuous in nature.

“Filament-forming composition” and/or “fibrous element-formingcomposition” as used herein means a composition that is suitable formaking a fibrous element of the present invention such as by meltblowingand/or spunbonding. The filament-forming composition comprises one ormore filament-forming materials that exhibit properties that make themsuitable for spinning into a fibrous element. In one example, thefilament-forming material comprises a polymer. In addition to one ormore filament-forming materials, the filament-forming composition maycomprise one or more additives, for example one or more active agents.In addition, the filament-forming composition may comprise one or morepolar solvents, such as water, into which one or more, for example all,of the filament-forming materials and/or one or more, for example all,of the active agents are dissolved and/or dispersed prior to spinning afibrous element, such as a filament from the filament-formingcomposition.

In one example as shown in FIG. 5, a filament 16 of the presentinvention made from a filament-forming composition of the presentinvention is such that one or more additives 18, for example one or moreactive agents, may be present in the filament rather than on thefilament, such as a coating composition comprising one or more activeagents, which may be the same or different from the active agents in thefibrous elements and/or particles. The total level of filament-formingmaterials and total level of active agents present in thefilament-forming composition may be any suitable amount so long as thefibrous elements of the present invention are produced therefrom.

In one example, one or more additives, such as active agents, may bepresent in the fibrous element and one or more additional additives,such as active agents, may be present on a surface of the fibrouselement. In another example, a fibrous element of the present inventionmay comprise one or more additives, such as active agents, that arepresent in the fibrous element when originally made, but then bloom to asurface of the fibrous element prior to and/or when exposed toconditions of intended use of the fibrous element.

“Filament-forming material” as used herein means a material, such as apolymer or monomers capable of producing a polymer that exhibitsproperties suitable for making a fibrous element. In one example, thefilament-forming material comprises one or more substituted polymerssuch as an anionic, cationic, zwitterionic, and/or nonionic polymer. Inanother example, the polymer may comprise a hydroxyl polymer, such as apolyvinyl alcohol (“PVOH”), a partially hydrolyzed polyvinyl acetateand/or a polysaccharide, such as starch and/or a starch derivative, suchas an ethoxylated starch and/or acid-thinned starch,carboxymethylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose.In another example, the polymer may comprise polyethylenes and/orterephthalates. In yet another example, the filament-forming material isa polar solvent-soluble material.

“Particle” as used herein means a solid additive, such as a powder,granule, encapsulate, microcapsule, and/or prill. In one example, theparticle exhibits a median particle size of 1600 μm or less as measuredaccording to the Median Particle Size Test Method described herein. Inanother example, the particle exhibits a median particle size of fromabout 1 μm to about 1600 μm and/or from about 1 μm to about 800 μmand/or from about 5 μm to about 500 μm and/or from about 10 μm to about300 μm and/or from about 10 μm to about 100 μm and/or from about 10 μmto about 50 μm and/or from about 10 μm to about 30 μm as measuredaccording to the Median Particle Size Test Method described herein. Theshape of the particle can be in the form of spheres, rods, plates,tubes, squares, rectangles, discs, stars, fibers or have regular orirregular random forms.

“Active agent-containing particle” as used herein means a solid additivecomprising one or more active agents. In one example, the activeagent-containing particle is an active agent in the form of a particle(in other words, the particle comprises 100% active agent(s)). Theactive agent-containing particle may exhibit a median particle size of1600 μm or less as measured according to the Median Particle Size TestMethod described herein. In another example, the active agent-containingparticle exhibits a median particle size of from about 1 μm to about1600 μm and/or from about 1 μm to about 800 μm and/or from about 5 μm toabout 500 μm and/or from about 10 μm to about 300 μm and/or from about10 μm to about 100 μm and/or from about 10 μm to about 50 μm and/or fromabout 10 μm to about 30 μm as measured according to the Median ParticleSize Test Method described herein. In one example, one or more of theactive agents is in the form of a particle that exhibits a medianparticle size of 20 μm or less as measured according to the MedianParticle Size Test Method described herein.

In one example of the present invention, the fibrous structure comprisesa plurality of particles, for example active agent-containing particles,and a plurality of fibrous elements in a weight ratio of particles, forexample active agent-containing particles, to fibrous elements of 1:100or greater and/or 1:50 or greater and/or 1:10 or greater and/or 1:3 orgreater and/or 1:2 or greater and/or 1:1 or greater and/or from about7:1 to about 1:100 and/or from about 7:1 to about 1:50 and/or from about7:1 to about 1:10 and/or from about 7:1 to about 1:3 and/or from about6:1 to 1:2 and/or from about 5:1 to about 1:1 and/or from about 4:1 toabout 1:1 and/or from about 3:1 to about 1.5:1.

In another example of the present invention, the fibrous structurecomprises a plurality of particles, for example active agent-containingparticles, and a plurality of fibrous elements in a weight ratio ofparticles, for example active agent-containing particles, to fibrouselements of from about 7:1 to about 1:1 and/or from about 7:1 to about1.5:1 and/or from about 7:1 to about 3:1 and/or from about 6:1 to about3:1.

In yet another example of the present invention, the fibrous structurecomprises a plurality of particles, for example active agent-containingparticles, and a plurality of fibrous elements in a weight ratio ofparticles, for example active agent-containing particles, to fibrouselements of from about 1:1 to about 1:100 and/or from about 1:2 to about1:50 and/or from about 1:3 to about 1:50 and/or from about 1:3 to about1:10.

In another example, the fibrous structure of the present inventioncomprises a plurality of particles, for example active agent-containingparticles, at a basis weight of greater than 1 g/m² and/or greater than10 g/m² and/or greater than 20 g/m² and/or greater than 30 g/m² and/orgreater than 40 g/m² and/or from about 1 g/m² to about 5000 g/m² and/orto about 3500 g/m² and/or to about 2000 g/m² and/or from about 1 g/m² toabout 1000 g/m² and/or from about 10 g/m² to about 400 g/m² and/or fromabout 20 g/m² to about 300 g/m² and/or from about 30 g/m² to about 200g/m² and/or from about 40 g/m² to about 100 g/m² as measured by theBasis Weight Test Method described herein.

In another example, the fibrous structure of the present inventioncomprises a plurality of fibrous elements at a basis weight of greaterthan 1 g/m² and/or greater than 10 g/m² and/or greater than 20 g/m²and/or greater than 30 g/m² and/or greater than 40 g/m² and/or fromabout 1 g/m² to about 3000 g/m² and/or from about 10 g/m² to about 5000g/m² and/or to about 3000 g/m² and/or to about 2000 g/m² and/or fromabout 20 g/m² to about 2000 g/m² and/or from about 30 g/m² to about 1000g/m² and/or from about 30 g/m² to about 500 g/m² and/or from about 30g/m² to about 300 g/m² and/or from about 40 g/m² to about 100 g/m²and/or from about 40 g/m² to about 80 g/m² as measured by the BasisWeight Test Method described herein. In one example, the fibrousstructure comprises two or more layers wherein fibrous elements arepresent in at least one of the layers at a basis weight of from about 1g/m² to about 300 g/m².

“Additive” as used herein means any material present in the fibrouselement of the present invention that is not a filament-formingmaterial. In one example, an additive comprises an active agent. Inanother example, an additive comprises a processing aid. In stillanother example, an additive comprises a filler. In one example, anadditive comprises any material present in the fibrous element that itsabsence from the fibrous element would not result in the fibrous elementlosing its fibrous element structure, in other words, its absence doesnot result in the fibrous element losing its solid form. In anotherexample, an additive, for example an active agent, comprises anon-polymer material.

In another example, an additive may comprise a plasticizer for thefibrous element. Non-limiting examples of suitable plasticizers for thepresent invention include polyols, copolyols, polycarboxylic acids,polyesters and dimethicone copolyols. Examples of useful polyolsinclude, but are not limited to, glycerin, diglycerin, propylene glycol,ethylene glycol, butylene glycol, pentylene glycol, cyclohexanedimethanol, hexanediol, 2,2,4-trimethylpentane-1,3-diol, polyethyleneglycol (200-600), pentaerythritol, sugar alcohols such as sorbitol,manitol, lactitol and other mono- and polyhydric low molecular weightalcohols (e.g., C2-C8 alcohols); mono di- and oligo-saccharides such asfructose, glucose, sucrose, maltose, lactose, high fructose corn syrupsolids, and dextrins, and ascorbic acid.

In one example, the plasticizer includes glycerin and/or propyleneglycol and/or glycerol derivatives such as propoxylated glycerol. Instill another example, the plasticizer is selected from the groupconsisting of glycerin, ethylene glycol, polyethylene glycol, propyleneglycol, glycidol, urea, sorbitol, xylitol, maltitol, sugars, ethylenebisformamide, amino acids, and mixtures thereof.

In another example, an additive may comprise a rheology modifier, suchas a shear modifier and/or an extensional modifier. Non-limitingexamples of rheology modifiers include but not limited topolyacrylamide, polyurethanes and polyacrylates that may be used in thefibrous elements of the present invention. Non-limiting examples ofrheology modifiers are commercially available from The Dow ChemicalCompany (Midland, Mich.).

In yet another example, an additive may comprise one or more colorsand/or dyes that are incorporated into the fibrous elements of thepresent invention to provide a visual signal when the fibrous elementsare exposed to conditions of intended use and/or when an active agent isreleased from the fibrous elements and/or when the fibrous element'smorphology changes.

In still yet another example, an additive may comprise one or morerelease agents and/or lubricants. Non-limiting examples of suitablerelease agents and/or lubricants include fatty acids, fatty acid salts,fatty alcohols, fatty esters, sulfonated fatty acid esters, fatty amineacetates, fatty amide, silicones, aminosilicones, fluoropolymers, andmixtures thereof. In one example, the release agents and/or lubricantsmay be applied to the fibrous element, in other words, after the fibrouselement is formed. In one example, one or more release agents/lubricantsmay be applied to the fibrous element prior to collecting the fibrouselements on a collection device to form a fibrous structure. In anotherexample, one or more release agents/lubricants may be applied to afibrous structure formed from the fibrous elements of the presentinvention prior to contacting one or more fibrous structures, such as ina stack of fibrous structures. In yet another example, one or morerelease agents/lubricants may be applied to the fibrous element of thepresent invention and/or fibrous structure comprising the fibrouselement prior to the fibrous element and/or fibrous structure contactinga surface, such as a surface of equipment used in a processing system soas to facilitate removal of the fibrous element and/or fibrous structureand/or to avoid layers of fibrous elements and/or plies of fibrousstructures of the present invention sticking to one another, eveninadvertently. In one example, the release agents/lubricants compriseparticulates.

In even still yet another example, an additive may comprise one or moreanti-blocking and/or detackifying agents. Non-limiting examples ofsuitable anti-blocking and/or detackifying agents include starches,starch derivatives, crosslinked polyvinylpyrrolidone, crosslinkedcellulose, microcrystalline cellulose, silica, metallic oxides, calciumcarbonate, talc, mica, and mixtures thereof.

“Conditions of intended use” as used herein means the temperature,physical, chemical, and/or mechanical conditions that a fibrous elementand/or particle and/or fibrous structure of the present invention isexposed to when the fibrous element and/or particle and/or fibrousstructure is used for one or more of its designed purposes. For example,if a fibrous element and/or a particle and/or a fibrous structurecomprising a fibrous element is designed to be used in a washing machinefor laundry care purposes, the conditions of intended use will includethose temperature, chemical, physical and/or mechanical conditionspresent in a washing machine, including any wash water, during a laundrywashing operation. In another example, if a fibrous element and/or aparticle and/or a fibrous structure comprising a fibrous element isdesigned to be used by a human as a shampoo for hair care purposes, theconditions of intended use will include those temperature, chemical,physical and/or mechanical conditions present during the shampooing ofthe human's hair. Likewise, if a fibrous element and/or a particleand/or a fibrous structure comprising a fibrous element is designed tobe used in a dishwashing operation, by hand or by a dishwashing machine,the conditions of intended use will include the temperature, chemical,physical and/or mechanical conditions present in a dishwashing waterand/or dishwashing machine, during the dishwashing operation.

“Active agent” as used herein means an additive that produces anintended effect in an environment external to a fibrous element and/or aparticle and/or a fibrous structure comprising a fibrous element of thepresent invention, such as when the fibrous element and/or a particleand/or fibrous structure is exposed to conditions of intended use of thefibrous element and/or a particle and/or a fibrous structure comprisinga fibrous element. In one example, an active agent comprises an additivethat treats a surface, such as a hard surface (i.e., kitchencountertops, bath tubs, toilets, toilet bowls, sinks, floors, walls,teeth, cars, windows, mirrors, dishes) and/or a soft surface (i.e.,fabric, hair, skin, carpet, crops, plants). In another example, anactive agent comprises an additive that creates a chemical reaction(i.e., foaming, fizzing, coloring, warming, cooling, lathering,disinfecting and/or clarifying and/or chlorinating, such as inclarifying water and/or disinfecting water and/or chlorinating water).In yet another example, an active agent comprises an additive thattreats an environment (i.e., deodorizes, purifies, perfumes air). In oneexample, the active agent is formed in situ, such as during theformation of the fibrous element and/or particle containing the activeagent, for example the fibrous element and/or particle may comprise awater-soluble polymer (e.g., starch) and a surfactant (e.g., anionicsurfactant), which may create a polymer complex or coacervate thatfunctions as the active agent used to treat fabric surfaces.

“Treats” as used herein with respect to treating a surface means thatthe active agent provides a benefit to a surface or environment. Treatsincludes regulating and/or immediately improving a surface's orenvironment's appearance, cleanliness, smell, purity and/or feel. In oneexample treating in reference to treating a keratinous tissue (forexample skin and/or hair) surface means regulating and/or immediatelyimproving the keratinous tissue's cosmetic appearance and/or feel. Forinstance, “regulating skin, hair, or nail (keratinous tissue) condition”includes: thickening of skin, hair, or nails (e.g, building theepidermis and/or dermis and/or sub-dermal [e.g., subcutaneous fat ormuscle] layers of the skin, and where applicable the keratinous layersof the nail and hair shaft) to reduce skin, hair, or nail atrophy,increasing the convolution of the dermal-epidermal border (also known asthe rete ridges), preventing loss of skin or hair elasticity (loss,damage and/or inactivation of functional skin elastin) such aselastosis, sagging, loss of skin or hair recoil from deformation;melanin or non-melanin change in coloration to the skin, hair, or nailssuch as under eye circles, blotching (e.g., uneven red coloration dueto, e.g., rosacea) (hereinafter referred to as “red blotchiness”),sallowness (pale color), discoloration caused by telangiectasia orspider vessels, and graying hair.

In another example, treating means removing stains and/or odors fromfabric articles, such as clothes, towels, linens, and/or hard surfaces,such as countertops and/or dishware including pots and pans.

“Fabric care active agent” as used herein means an active agent thatwhen applied to a fabric provides a benefit and/or improvement to thefabric. Non-limiting examples of benefits and/or improvements to afabric include cleaning (for example by surfactants), stain removal,stain reduction, wrinkle removal, color restoration, static control,wrinkle resistance, permanent press, wear reduction, wear resistance,pill removal, pill resistance, soil removal, soil resistance (includingsoil release), shape retention, shrinkage reduction, softness,fragrance, anti-bacterial, anti-viral, odor resistance, and odorremoval.

“Dishwashing active agent” as used herein means an active agent thatwhen applied to dishware, glassware, pots, pans, utensils, and/orcooking sheets provides a benefit and/or improvement to the dishware,glassware, plastic items, pots, pans and/or cooking sheets. Non-limitingexamples of benefits and/or improvements to the dishware, glassware,plastic items, pots, pans, utensils, and/or cooking sheets include foodand/or soil removal, cleaning (for example by surfactants) stainremoval, stain reduction, grease removal, water spot removal and/orwater spot prevention, glass and metal care, sanitization, shining, andpolishing.

“Hard surface active agent” as used herein means an active agent whenapplied to floors, countertops, sinks, windows, mirrors, showers, baths,and/or toilets provides a benefit and/or improvement to the floors,countertops, sinks, windows, mirrors, showers, baths, and/or toilets.Non-limiting examples of benefits and/or improvements to the floors,countertops, sinks, windows, mirrors, showers, baths, and/or toiletsinclude food and/or soil removal, cleaning (for example by surfactants),stain removal, stain reduction, grease removal, water spot removaland/or water spot prevention, limescale removal, disinfection, shining,polishing, and freshening.

“Weight ratio” as used herein means the ratio between two materials ontheir dry basis. For example, the weight ratio of filament-formingmaterials to active agents within a fibrous element is the ratio of theweight of filament-forming material on a dry weight basis (g or %) inthe fibrous element to the weight of additive, such as active agent(s)on a dry weight basis (g or %—same units as the filament-formingmaterial weight) in the fibrous element. In another example, the weightratio of particles to fibrous elements within a fibrous structure is theratio of the weight of particles on a dry weight basis (g or %) in thefibrous structure to the weight of fibrous elements on a dry weightbasis (g or %—same units as the particle weight) in the fibrousstructure.

“Water-soluble material” as used herein means a material that ismiscible in water. In other words, a material that is capable of forminga stable (does not separate for greater than 5 minutes after forming thehomogeneous solution) homogeneous solution with water at ambientconditions.

“Ambient conditions” as used herein means 23° C.±1.0° C. and a relativehumidity of 50%±2%.

“Weight average molecular weight” as used herein means the weightaverage molecular weight as determined using gel permeationchromatography according to the protocol found in Colloids and SurfacesA. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pg. 107-121.

“Length” as used herein, with respect to a fibrous element, means thelength along the longest axis of the fibrous element from one terminusto the other terminus. If a fibrous element has a kink, curl or curvesin it, then the length is the length along the entire path of thefibrous element from one terminus to the other terminus.

“Diameter” as used herein, with respect to a fibrous element, ismeasured according to the Diameter Test Method described herein. In oneexample, a fibrous element of the present invention exhibits a diameterof less than 100 μm and/or less than 75 μm and/or less than 50 μm and/orless than 25 μm and/or less than 20 μm and/or less than 15 μm and/orless than 10 μm and/or less than 6 μm and/or greater than 1 μm and/orgreater than 3 μm.

“Triggering condition” as used herein in one example means anything, asan act or event, that serves as a stimulus and initiates or precipitatesa change in the fibrous element and/or particle and/or fibrous structureof the present invention, such as a loss or altering of the fibrouselement's and/or fibrous structure's physical structure and/or a releaseof an additive, such as an active agent therefrom. In another example,the triggering condition may be present in an environment, such aswater, when a fibrous element and/or particle and/or fibrous structureof the present invention is added to the water. In other words, nothingchanges in the water except for the fact that the fibrous element and/orfibrous structure of the present invention is added to the water.

“Morphology changes” as used herein with respect to a fibrous element'sand/or particle's morphology changing means that the fibrous elementexperiences a change in its physical structure. Non-limiting examples ofmorphology changes for a fibrous element and/or particle of the presentinvention include dissolution, melting, swelling, shrinking, breakinginto pieces, exploding, lengthening, shortening, and combinationsthereof. The fibrous elements and/or particles of the present inventionmay completely or substantially lose their fibrous element or particlephysical structure or they may have their morphology changed or they mayretain or substantially retain their fibrous element or particlephysical structure as they are exposed to conditions of intended use.

“By weight on a dry fibrous element basis” and/or “by weight on a dryparticle basis” and/or “by weight on a dry fibrous structure basis”means the weight of the fibrous element and/or particle and/or fibrousstructure, respectively, measured immediately after the fibrous elementand/or particle and/or fibrous structure, respectively, has beenconditioned in a conditioned room at a temperature of 23° C.±1.0° C. anda relative humidity of 50%±10% for 2 hours. In one example, by weight ona dry fibrous element basis and/or dry particle basis and/or dry fibrousstructure basis means that the fibrous element and/or particle and/orfibrous structure comprises less than 20% and/or less than 15% and/orless than 10% and/or less than 7% and/or less than 5% and/or less than3% and/or to 0% and/or to greater than 0% based on the dry weight of thefibrous element and/or particle and/or fibrous structure of moisture,such as water, for example free water, as measured according to theWater Content Test Method described herein.

“Total level” as used herein, for example with respect to the totallevel of one or more active agents present in the fibrous element and/orparticle and/or fibrous structure, means the sum of the weights orweight percent of all of the subject materials, for example activeagents. In other words, a fibrous element and/or particle and/or fibrousstructure may comprise 25% by weight on a dry fibrous element basisand/or dry particle basis and/or dry fibrous structure basis of ananionic surfactant, 15% by weight on a dry fibrous element basis and/ordry particle basis and/or dry fibrous structure basis of a nonionicsurfactant, 10% by weight of a chelant on a dry fibrous element basisand/or dry particle basis and/or dry fibrous structure basis, and 5% byweight of a perfume a dry fibrous element basis and/or dry particlebasis and/or dry fibrous structure basis so that the total level ofactive agents present in the fibrous element and/or particle and/orfibrous structure is greater than 50%; namely 55% by weight on a dryfibrous element basis and/or dry particle basis and/or dry fibrousstructure basis.

“Fibrous structure product” as used herein means a solid form, forexample a rectangular solid, sometimes referred to as a sheet, thatcomprises one or more active agents, for example a fabric care activeagent, a dishwashing active agent, a hard surface active agent, andmixtures thereof. In one example, a fibrous structure product of thepresent invention comprises one or more surfactants, one or more enzymes(such as in the form of an enzyme prill), one or more perfumes and/orone or more suds suppressors. In another example, a fibrous structureproduct of the present invention comprises a builder and/or a chelatingagent. In another example, a fibrous structure product of the presentinvention comprises a bleaching agent (such as an encapsulated bleachingagent).

“Different from” or “different” as used herein means, with respect to amaterial, such as a fibrous element as a whole and/or a filament-formingmaterial within a fibrous element and/or an active agent within afibrous element, that one material, such as a fibrous element and/or afilament-forming material and/or an active agent, is chemically,physically and/or structurally different from another material, such asa fibrous element and/or a filament-forming material and/or an activeagent. For example, a filament-forming material in the form of afilament is different from the same filament-forming material in theform of a fiber. Likewise, a starch polymer is different from acellulose polymer. However, different molecular weights of the samematerial, such as different molecular weights of a starch, are notdifferent materials from one another for purposes of the presentinvention.

“Random mixture of polymers” as used herein means that two or moredifferent filament-forming materials are randomly combined to form afibrous element. Accordingly, two or more different filament-formingmaterials that are orderly combined to form a fibrous element, such as acore and sheath bicomponent fibrous element, is not a random mixture ofdifferent filament-forming materials for purposes of the presentinvention.

“Associate,” “Associated,” “Association,” and/or “Associating” as usedherein with respect to fibrous elements and/or particle means combining,either in direct contact or in indirect contact, fibrous elements and/orparticles such that a fibrous structure is formed. In one example, theassociated fibrous elements and/or particles may be bonded together forexample by adhesives and/or thermal bonds. In another example, thefibrous elements and/or particles may be associated with one another bybeing deposited onto the same fibrous structure making belt and/orpatterned belt.

“Machine Direction” or “MD” as used herein means the direction parallelto the flow of the fibrous structure through the fibrous structuremaking machine and/or fibrous structure product manufacturing equipment.

“Cross Machine Direction” or “CD” as used herein means the directionperpendicular to the machine direction in the same plane of the fibrousstructure and/or fibrous structure product comprising the fibrousstructure.

“Ply” or “Plies” as used herein means an individual fibrous structureoptionally to be disposed in a substantially contiguous, face-to-facerelationship with other plies, forming a multiple ply fibrous structure.It is also contemplated that a single fibrous structure can effectivelyform two “plies” or multiple “plies”, for example, by being folded onitself.

As used herein, the articles “a” and “an” when used herein, for example,“an anionic surfactant” or “a fiber” is understood to mean one or moreof the material that is claimed or described.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

Unless otherwise noted, all component or composition levels are inreference to the active level of that component or composition, and areexclusive of impurities, for example, residual solvents or by-products,which may be present in commercially available sources.

Fibrous Structure

The fibrous structure of the present invention comprises a plurality offibrous elements, for example a plurality of filaments, and one or moreparticles, for example one or more active agent-containing particles,such as water-soluble, active agent-containing particles.

In one example, the fibrous elements and/or particles may be arrangedwithin the fibrous structure to provide the fibrous structure with twoor more regions that comprise different active agents. For example, oneregion of the fibrous structure may comprise bleaching agents and/orsurfactants and another region of the fibrous structure may comprisesoftening agents.

As shown in FIG. 5, an example of a fibrous structure 28 according tothe present invention comprises a first layer 30 comprising a pluralityof fibrous elements 32, in this case filaments, a second layer 34comprising a plurality of fibrous elements 32, in this case filaments,and a plurality of particles 36 positioned between the first and secondlayers 30 and 34. A similar fibrous structure can be formed bydepositing a plurality of particles on a surface of a first ply offibrous structure comprising a plurality of fibrous elements and thenassociating a second ply of fibrous structure comprising a plurality offibrous elements such that the particles are positioned between thefirst and second plies.

As shown in FIG. 6, another example of a fibrous structure 28 of thepresent invention comprises a first layer 30 comprising a plurality offibrous elements 32, in this case filaments, wherein the first layer 30comprises one or more pockets 38 (also referred to as recesses), whichmay be in a non-random, repeating pattern. One or more of the pockets 38may contain one or more particles 36. The fibrous structure 28 furthercomprises a second layer 34 that is associated with the first layer 30such that the particles 36 are entrapped in the pockets 38. Like above,a similar fibrous structure can be formed by depositing a plurality ofparticles in pockets of a first ply of fibrous structure comprising aplurality of fibrous elements and then associating a second ply offibrous structure comprising a plurality of fibrous elements such thatthe particles are entrapped within the pockets of the first ply. In oneexample, the pockets may be separated from the fibrous structure toproduce discrete pockets.

As shown in FIG. 7, an example of a multi-ply fibrous structure 40 ofthe present invention comprises a first ply 42 of a fibrous structureaccording to FIG. 6 above and a second ply 44 of fibrous structureassociated with the first ply 42, wherein the second ply 44 comprises aplurality of fibrous elements 32, in this case filaments, and aplurality of particles 36 dispersed, in this case randomly, in the x, y,and z axes, throughout the fibrous structure.

As shown in FIG. 8, an example of a fibrous structure 28 of the presentinvention comprises a plurality of fibrous elements 32, in this casefilaments, and a plurality of particles 36 dispersed, in this caserandomly, in the x, y, and z axes, throughout the fibrous structure 28.

Even though the fibrous element and/or fibrous structure of the presentinvention are in solid form, the filament-forming composition used tomake the fibrous elements of the present invention may be in the form ofa liquid.

In one example, the fibrous structure comprises a plurality of identicalor substantially identical from a compositional perspective of fibrouselements according to the present invention. In another example, thefibrous structure may comprise two or more different fibrous elementsaccording to the present invention. Non-limiting examples of differencesin the fibrous elements may be physical differences such as differencesin diameter, length, texture, shape, rigidness, elasticity, and thelike; chemical differences such as crosslinking level, solubility,melting point, Tg, active agent, filament-forming material, color, levelof active agent, basis weight, level of filament-forming material,presence of any coating on fibrous element, biodegradable or not,hydrophobic or not, contact angle, and the like; differences in whetherthe fibrous element loses its physical structure when the fibrouselement is exposed to conditions of intended use; differences in whetherthe fibrous element's morphology changes when the fibrous element isexposed to conditions of intended use; and differences in rate at whichthe fibrous element releases one or more of its active agents when thefibrous element is exposed to conditions of intended use. In oneexample, two or more fibrous elements and/or particles within thefibrous structure may comprise different active agents. This may be thecase where the different active agents may be incompatible with oneanother, for example an anionic surfactant (such as a shampoo activeagent) and a cationic surfactant (such as a hair conditioner activeagent).

In another example, the fibrous structure may exhibit different regions,such as different regions of basis weight, density and/or caliper. Inyet another example, the fibrous structure may comprise texture on oneor more of its surfaces. A surface of the fibrous structure may comprisea pattern, such as a non-random, repeating pattern. The fibrousstructure may be embossed with an emboss pattern. In another example,the fibrous structure may comprise apertures. The apertures may bearranged in a non-random, repeating pattern.

In one example, the fibrous structure may comprise discrete regions offibrous elements that differ from other parts of the fibrous structure.

Non-limiting examples of use of the fibrous structure of the presentinvention include, but are not limited to a laundry dryer substrate,washing machine substrate, washcloth, hard surface cleaning and/orpolishing substrate, floor cleaning and/or polishing substrate, as acomponent in a battery, baby wipe, adult wipe, feminine hygiene wipe,bath tissue wipe, window cleaning substrate, oil containment and/orscavenging substrate, insect repellant substrate, swimming pool chemicalsubstrate, food, breath freshener, deodorant, waste disposal bag,packaging film and/or wrap, wound dressing, medicine delivery, buildinginsulation, crops and/or plant cover and/or bedding, glue substrate,skin care substrate, hair care substrate, air care substrate, watertreatment substrate and/or filter, toilet bowl cleaning substrate, candysubstrate, pet food, livestock bedding, teeth whitening substrates,carpet cleaning substrates, and other suitable uses of the active agentsof the present invention.

The fibrous structure of the present invention may be used as is or maybe coated with one or more active agents.

In one example, the fibrous structure of the present invention exhibitsa dissolution time of less than 24 hours and/or less than 12 hoursand/or less than 6 hours and/or less than 1 hour (3600 seconds) and/orless than 30 minutes and/or less than 25 minutes and/or less than 20minutes and/or less than 15 minutes and/or less than 10 minutes and/orless than 5 minutes and/or greater than 1 second and/or greater than 5seconds and/or greater than 10 seconds and/or greater than 30 secondsand/or greater than 1 minute as measured according to the DissolutionTest Method described herein.

In one example, the fibrous structure of the present invention exhibitsan average dissolution time per gsm of sample of about 10 seconds/gsm(s/gsm) or less, and/or about 5.0 s/gsm or less, and/or about 3.0 s/gsmor less, and/or about 2.0 s/gsm or less, and/or about 1.8 s/gsm or less,and/or about 1.5 s/gsm or less as measured according to the DissolutionTest Method described herein.

In one example, the fibrous structure of the present invention exhibitsa thickness of greater than 0.01 mm and/or greater than 0.05 mm and/orgreater than 0.1 mm and/or to about 100 mm and/or to about 50 mm and/orto about 20 mm and/or to about 10 mm and/or to about 5 mm and/or toabout 2 mm and/or to about 0.5 mm and/or to about 0.3 mm as measured bythe Thickness Test Method described herein.

Non-limiting examples of other fibrous structures suitable for thepresent invention are disclosed in U.S. Provisional Patent ApplicationNo. 61/583,011 and 61/583,016 filed Jan. 4, 2012 are hereby incorporatedby reference herein.

Particles

The particles may be water-soluble or water-insoluble. In one example,one group of particles may be water-soluble and a different group ofparticles may be water-insoluble. In another example, the particles maycomprise one or more active agents (in other words, the particles maycomprises active agent-containing particles). In still another example,the particles may consist essentially of and/or consist of one or moreactive agents (in other words, the particles may comprise 100% or about100% by weight on a dry particle basis of one or more active agents). Instill another example, the particles may comprise water-solubleparticles. In yet another example, the particles may comprisewater-soluble, active agent-containing particles.

Fibrous Elements

The fibrous elements may be water-soluble or water-insoluble. In oneexample, the fibrous elements comprise one or more filament-formingmaterials. In another example, the fibrous elements comprise one or moreactive agents. In still another example, the fibrous elements compriseone or more filament-forming materials and one or more active agents. Inanother example, the fibrous elements may comprise water-soluble fibrouselements.

The fibrous element, such as a filament and/or fiber, of the presentinvention comprises one or more filament-forming materials. In additionto the filament-forming materials, the fibrous element may furthercomprise one or more active agents that are releasable from the fibrouselement, such as when the fibrous element and/or fibrous structurecomprising the fibrous element is exposed to conditions of intended use.In one example, the total level of the one or more filament-formingmaterials present in the fibrous element is less than 80% by weight on adry fibrous element basis and/or dry fibrous structure basis and thetotal level of the one or more active agents present in the fibrouselement is greater than 20% by weight on a dry fibrous element basisand/or dry fibrous structure basis.

In one example, the fibrous element of the present invention comprisesabout 100% and/or greater than 95% and/or greater than 90% and/orgreater than 85% and/or greater than 75% and/or greater than 50% byweight on a dry fibrous element basis and/or dry fibrous structure basisof one or more filament-forming materials. For example, thefilament-forming material may comprise polyvinyl alcohol, starch,carboxymethylcellulose, and other suitable polymers, especially hydroxylpolymers.

In another example, the fibrous element of the present inventioncomprises one or more filament-forming materials and one or more activeagents wherein the total level of filament-forming materials present inthe fibrous element is from about 5% to less than 80% by weight on a dryfibrous element basis and/or dry fibrous structure basis and the totallevel of active agents present in the fibrous element is greater than20% to about 95% by weight on a dry fibrous element basis and/or dryfibrous structure basis.

In one example, the fibrous element of the present invention comprisesat least 10% and/or at least 15% and/or at least 20% and/or less thanless than 80% and/or less than 75% and/or less than 65% and/or less than60% and/or less than 55% and/or less than 50% and/or less than 45%and/or less than 40% by weight on a dry fibrous element basis and/or dryfibrous structure basis of the filament-forming materials and greaterthan 20% and/or at least 35% and/or at least 40% and/or at least 45%and/or at least 50% and/or at least 60% and/or less than 95% and/or lessthan 90% and/or less than 85% and/or less than 80% and/or less than 75%by weight on a dry fibrous element basis and/or dry fibrous structurebasis of active agents.

In one example, the fibrous element of the present invention comprisesat least 5% and/or at least 10% and/or at least 15% and/or at least 20%and/or less than 50% and/or less than 45% and/or less than 40% and/orless than 35% and/or less than 30% and/or less than 25% by weight on adry fibrous element basis and/or dry fibrous structure basis of thefilament-forming materials and greater than 50% and/or at least 55%and/or at least 60% and/or at least 65% and/or at least 70% and/or lessthan 95% and/or less than 90% and/or less than 85% and/or less than 80%and/or less than 75% by weight on a dry fibrous element basis and/or dryfibrous structure basis of active agents. In one example, the fibrouselement of the present invention comprises greater than 80% by weight ona dry fibrous element basis and/or dry fibrous structure basis of activeagents.

In another example, the one or more filament-forming materials andactive agents are present in the fibrous element at a weight ratio oftotal level of filament-forming materials to active agents of 4.0 orless and/or 3.5 or less and/or 3.0 or less and/or 2.5 or less and/or 2.0or less and/or 1.85 or less and/or less than 1.7 and/or less than 1.6and/or less than 1.5 and/or less than 1.3 and/or less than 1.2 and/orless than 1 and/or less than 0.7 and/or less than 0.5 and/or less than0.4 and/or less than 0.3 and/or greater than 0.1 and/or greater than0.15 and/or greater than 0.2.

In still another example, the fibrous element of the present inventioncomprises from about 10% and/or from about 15% to less than 80% byweight on a dry fibrous element basis and/or dry fibrous structure basisof a filament-forming material, such as polyvinyl alcohol polymer,starch polymer, and/or carboxymethylcellulose polymer, and greater than20% to about 90% and/or to about 85% by weight on a dry fibrous elementbasis and/or dry fibrous structure basis of an active agent. The fibrouselement may further comprise a plasticizer, such as glycerin and/or pHadjusting agents, such as citric acid.

In yet another example, the fibrous element of the present inventioncomprises from about 10% and/or from about 15% to less than 80% byweight on a dry fibrous element basis and/or dry fibrous structure basisof a filament-forming material, such as polyvinyl alcohol polymer,starch polymer, and/or carboxymethylcellulose polymer, and greater than20% to about 90% and/or to about 85% by weight on a dry fibrous elementbasis and/or dry fibrous structure basis of an active agent, wherein theweight ratio of filament-forming material to active agent is 4.0 orless. The fibrous element may further comprise a plasticizer, such asglycerin and/or pH adjusting agents, such as citric acid.

In even another example of the present invention, a fibrous elementcomprises one or more filament-forming materials and one or more activeagents selected from the group consisting of: enzymes, bleaching agents,builder, chelants, sensates, dispersants, and mixtures thereof that arereleasable and/or released when the fibrous element and/or fibrousstructure comprising the fibrous element is exposed to conditions ofintended use. In one example, the fibrous element comprises a totallevel of filament-forming materials of less than 95% and/or less than90% and/or less than 80% and/or less than 50% and/or less than 35%and/or to about 5% and/or to about 10% and/or to about 20% by weight ona dry fibrous element basis and/or dry fibrous structure basis and atotal level of active agents selected from the group consisting of:enzymes, bleaching agents, builder, chelants, perfumes, antimicrobials,antibacterials, antifungals, and mixtures thereof of greater than 5%and/or greater than 10% and/or greater than 20% and/or greater than 35%and/or greater than 50% and/or greater than 65% and/or to about 95%and/or to about 90% and/or to about 80% by weight on a dry fibrouselement basis and/or dry fibrous structure basis. In one example, theactive agent comprises one or more enzymes. In another example, theactive agent comprises one or more bleaching agents. In yet anotherexample, the active agent comprises one or more builders. In stillanother example, the active agent comprises one or more chelants. Instill another example, the active agent comprises one or more perfumes.In even still another example, the active agent comprise one or moreantimicrobials, antibacterials, and/or antifungals.

In yet another example of the present invention, the fibrous elements ofthe present invention may comprise active agents that may create healthand/or safety concerns if they become airborne. For example, the fibrouselement may be used to inhibit enzymes within the fibrous element frombecoming airborne.

In one example, the fibrous elements of the present invention may bemeltblown fibrous elements. In another example, the fibrous elements ofthe present invention may be spunbond fibrous elements. In anotherexample, the fibrous elements may be hollow fibrous elements prior toand/or after release of one or more of its active agents.

The fibrous elements of the present invention may be hydrophilic orhydrophobic. The fibrous elements may be surface treated and/orinternally treated to change the inherent hydrophilic or hydrophobicproperties of the fibrous element.

In one example, the fibrous element exhibits a diameter of less than 100μm and/or less than 75 μm and/or less than 50 μm and/or less than 25 μmand/or less than 10 μm and/or less than 5 μm and/or less than 1 μm asmeasured according to the Diameter Test Method described herein. Inanother example, the fibrous element of the present invention exhibits adiameter of greater than 1 μm as measured according to the Diameter TestMethod described herein. The diameter of a fibrous element of thepresent invention may be used to control the rate of release of one ormore active agents present in the fibrous element and/or the rate ofloss and/or altering of the fibrous element's physical structure.

The fibrous element may comprise two or more different active agents. Inone example, the fibrous element comprises two or more different activeagents, wherein the two or more different active agents are compatiblewith one another. In another example, the fibrous element comprises twoor more different active agents, wherein the two or more differentactive agents are incompatible with one another.

In one example, the fibrous element may comprise an active agent withinthe fibrous element and an active agent on an external surface of thefibrous element, such as an active agent coating on the fibrous element.The active agent on the external surface of the fibrous element may bethe same or different from the active agent present in the fibrouselement. If different, the active agents may be compatible orincompatible with one another.

In one example, one or more active agents may be uniformly distributedor substantially uniformly distributed throughout the fibrous element.In another example, one or more active agents may be distributed asdiscrete regions within the fibrous element. In still another example,at least one active agent is distributed uniformly or substantiallyuniformly throughout the fibrous element and at least one other activeagent is distributed as one or more discrete regions within the fibrouselement. In still yet another example, at least one active agent isdistributed as one or more discrete regions within the fibrous elementand at least one other active agent is distributed as one or morediscrete regions different from the first discrete regions within thefibrous element.

Filament-Forming Material

The filament-forming material is any suitable material, such as apolymer or monomers capable of producing a polymer that exhibitsproperties suitable for making a filament, such as by a spinningprocess.

In one example, the filament-forming material may comprise a polarsolvent-soluble material, such as an alcohol-soluble material and/or awater-soluble material.

In another example, the filament-forming material may comprise anon-polar solvent-soluble material.

In still another example, the filament-forming material may comprise awater-soluble material and be free (less than 5% and/or less than 3%and/or less than 1% and/or 0% by weight on a dry fibrous element basisand/or dry fibrous structure basis) of water-insoluble materials.

In yet another example, the filament-forming material may be afilm-forming material. In still yet another example, thefilament-forming material may be synthetic or of natural origin and itmay be chemically, enzymatically, and/or physically modified.

In even another example of the present invention, the filament-formingmaterial may comprise a polymer selected from the group consisting of:polymers derived from acrylic monomers such as the ethylenicallyunsaturated carboxylic monomers and ethylenically unsaturated monomers,polyvinyl alcohol, polyvinylformamide, polyvinylamine, polyacrylates,polymethacrylates, copolymers of acrylic acid and methyl acrylate,polyvinylpyrrolidones, polyalkylene oxides, starch and starchderivatives, pullulan, gelatin, and cellulose derivatives (for example,hydroxypropylmethyl celluloses, methyl celluloses, carboxymethycelluloses).

In still another example, the filament-forming material may comprises apolymer selected from the group consisting of: polyvinyl alcohol,polyvinyl alcohol derivatives, starch, starch derivatives, cellulosederivatives, hemicellulose, hemicellulose derivatives, proteins, sodiumalginate, hydroxypropyl methylcellulose, chitosan, chitosan derivatives,polyethylene glycol, tetramethylene ether glycol, polyvinyl pyrrolidone,hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethylcellulose, and mixtures thereof.

In another example, the filament-forming material comprises a polymer isselected from the group consisting of: pullulan, hydroxypropylmethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, carboxymethylcellulose, sodium alginate, xanthan gum,tragacanth gum, guar gum, acacia gum, Arabic gum, polyacrylic acid,methylmethacrylate copolymer, carboxyvinyl polymer, dextrin, pectin,chitin, levan, elsinan, collagen, gelatin, zein, gluten, soy protein,casein, polyvinyl alcohol, carboxylated polyvinyl alcohol, sulfonatedpolyvinyl alcohol, starch, starch derivatives, hemicellulose,hemicellulose derivatives, proteins, chitosan, chitosan derivatives,polyethylene glycol, tetramethylene ether glycol, hydroxymethylcellulose, and mixtures thereof.

Water-Soluble Materials

Non-limiting examples of water-soluble materials include water-solublepolymers. The water-soluble polymers may be synthetic or naturaloriginal and may be chemically and/or physically modified. In oneexample, the polar solvent-soluble polymers exhibit a weight averagemolecular weight of at least 10,000 g/mol and/or at least 20,000 g/moland/or at least 40,000 g/mol and/or at least 80,000 g/mol and/or atleast 100,000 g/mol and/or at least 1,000,000 g/mol and/or at least3,000,000 g/mol and/or at least 10,000,000 g/mol and/or at least20,000,000 g/mol and/or to about 40,000,000 g/mol and/or to about30,000,000 g/mol.

Non-limiting examples of water-soluble polymers include water-solublehydroxyl polymers, water-soluble thermoplastic polymers, water-solublebiodegradable polymers, water-soluble non-biodegradable polymers andmixtures thereof. In one example, the water-soluble polymer comprisespolyvinyl alcohol. In another example, the water-soluble polymercomprises starch. In yet another example, the water-soluble polymercomprises polyvinyl alcohol and starch. In yet another example, thewater-soluble polymer comprises carboxymethyl cellulose. An yet inanother example, the polymer comprise carboxymethyl cellulose andpolyvinyl alcohol.

a. Water-Soluble Hydroxyl Polymers—

Non-limiting examples of water-soluble hydroxyl polymers in accordancewith the present invention include polyols, such as polyvinyl alcohol,polyvinyl alcohol derivatives, polyvinyl alcohol copolymers, starch,starch derivatives, starch copolymers, chitosan, chitosan derivatives,chitosan copolymers, cellulose derivatives such as cellulose ether andester derivatives, cellulose copolymers, hemicellulose, hemicellulosederivatives, hemicellulose copolymers, gums, arabinans, galactans,proteins, carboxymethylcellulose, and various other polysaccharides andmixtures thereof.

In one example, a water-soluble hydroxyl polymer of the presentinvention comprises a polysaccharide.

“Polysaccharides” as used herein means natural polysaccharides andpolysaccharide derivatives and/or modified polysaccharides. Suitablewater-soluble polysaccharides include, but are not limited to, starches,starch derivatives, chitosan, chitosan derivatives, cellulosederivatives, hemicellulose, hemicellulose derivatives, gums, arabinans,galactans and mixtures thereof. The water-soluble polysaccharide mayexhibit a weight average molecular weight of from about 10,000 to about40,000,000 g/mol and/or greater than 100,000 g/mol and/or greater than1,000,000 g/mol and/or greater than 3,000,000 g/mol and/or greater than3,000,000 to about 40,000,000 g/mol.

The water-soluble polysaccharides may comprise non-cellulose and/ornon-cellulose derivative and/or non-cellulose copolymer water-solublepolysaccharides. Such non-cellulose water-soluble polysaccharides may beselected from the group consisting of: starches, starch derivatives,chitosan, chitosan derivatives, hemicellulose, hemicellulosederivatives, gums, arabinans, galactans and mixtures thereof.

In another example, a water-soluble hydroxyl polymer of the presentinvention comprises a non-thermoplastic polymer.

The water-soluble hydroxyl polymer may have a weight average molecularweight of from about 10,000 g/mol to about 40,000,000 g/mol and/orgreater than 100,000 g/mol and/or greater than 1,000,000 g/mol and/orgreater than 3,000,000 g/mol and/or greater than 3,000,000 g/mol toabout 40,000,000 g/mol. Higher and lower molecular weight water-solublehydroxyl polymers may be used in combination with hydroxyl polymershaving a certain desired weight average molecular weight.

Well known modifications of water-soluble hydroxyl polymers, such asnatural starches, include chemical modifications and/or enzymaticmodifications. For example, natural starch can be acid-thinned,hydroxy-ethylated, hydroxy-propylated, and/or oxidized. In addition, thewater-soluble hydroxyl polymer may comprise dent corn starch.

Naturally occurring starch is generally a mixture of linear amylose andbranched amylopectin polymer of D-glucose units. The amylose is asubstantially linear polymer of D-glucose units joined by (1,4)-α-Dlinks. The amylopectin is a highly branched polymer of D-glucose unitsjoined by (1,4)-α-D links and (1,6)-α-D links at the branch points.Naturally occurring starch typically contains relatively high levels ofamylopectin, for example, corn starch (64-80% amylopectin), waxy maize(93-100% amylopectin), rice (83-84% amylopectin), potato (about 78%amylopectin), and wheat (73-83% amylopectin). Though all starches arepotentially useful herein, the present invention is most commonlypracticed with high amylopectin natural starches derived fromagricultural sources, which offer the advantages of being abundant insupply, easily replenishable and inexpensive.

As used herein, “starch” includes any naturally occurring unmodifiedstarches, modified starches, synthetic starches and mixtures thereof, aswell as mixtures of the amylose or amylopectin fractions; the starch maybe modified by physical, chemical, or biological processes, orcombinations thereof. The choice of unmodified or modified starch forthe present invention may depend on the end product desired. In oneembodiment of the present invention, the starch or starch mixture usefulin the present invention has an amylopectin content from about 20% toabout 100%, more typically from about 40% to about 90%, even moretypically from about 60% to about 85% by weight of the starch ormixtures thereof.

Suitable naturally occurring starches can include, but are not limitedto, corn starch, potato starch, sweet potato starch, wheat starch, sagopalm starch, tapioca starch, rice starch, soybean starch, arrow rootstarch, amioca starch, bracken starch, lotus starch, waxy maize starch,and high amylose corn starch. Naturally occurring starches particularly,corn starch and wheat starch, are the preferred starch polymers due totheir economy and availability.

Polyvinyl alcohols herein can be grafted with other monomers to modifyits properties. A wide range of monomers has been successfully graftedto polyvinyl alcohol. Non-limiting examples of such monomers includevinyl acetate, styrene, acrylamide, acrylic acid, 2-hydroxyethylmethacrylate, acrylonitrile, 1,3-butadiene, methyl methacrylate,methacrylic acid, maleic acid, itaconic acid, sodium vinylsulfonate,sodium allylsulfonate, sodium methylallyl sulfonate, sodiumphenylallylether sulfonate, sodium phenylmethallylether sulfonate,2-acrylamido-methyl propane sulfonic acid (AMPs), vinylidene chloride,vinyl chloride, vinyl amine and a variety of acrylate esters.

In one example, the water-soluble hydroxyl polymer is selected from thegroup consisting of: polyvinyl alcohols, hydroxymethylcelluloses,hydroxyethylcelluloses, hydroxypropylmethylcelluloses,carboxymethylcelluloses, and mixtures thereof. A non-limiting example ofa suitable polyvinyl alcohol includes those commercially available fromSekisui Specialty Chemicals America, LLC (Dallas, Tex.) under theCELVOL® trade name. Another non-limiting example of a suitable polyvinylalcohol includes G Polymer commercially available from Nippon Ghosei. Anon-limiting example of a suitable hydroxypropylmethylcellulose includesthose commercially available from the Dow Chemical Company (Midland,Mich.) under the METHOCEL® trade name including combinations with abovementioned polyvinyl alcohols.

b. Water-Soluble Thermoplastic Polymers—

Non-limiting examples of suitable water-soluble thermoplastic polymersinclude thermoplastic starch and/or starch derivatives, polylactic acid,polyhydroxyalkanoate, polycaprolactone, polyesteramides and certainpolyesters, and mixtures thereof.

The water-soluble thermoplastic polymers of the present invention may behydrophilic or hydrophobic. The water-soluble thermoplastic polymers maybe surface treated and/or internally treated to change the inherenthydrophilic or hydrophobic properties of the thermoplastic polymer.

The water-soluble thermoplastic polymers may comprise biodegradablepolymers.

Any suitable weight average molecular weight for the thermoplasticpolymers may be used. For example, the weight average molecular weightfor a thermoplastic polymer in accordance with the present invention isgreater than about 10,000 g/mol and/or greater than about 40,000 g/moland/or greater than about 50,000 g/mol and/or less than about 500,000g/mol and/or less than about 400,000 g/mol and/or less than about200,000 g/mol.

Active Agents

Active agents are a class of additives that are designed and intended toprovide a benefit to something other than the fibrous element and/orparticle and/or fibrous structure itself, such as providing a benefit toan environment external to the fibrous element and/or particle and/orfibrous structure. Active agents may be any suitable additive thatproduces an intended effect under intended use conditions of the fibrouselement. For example, the active agent may be selected from the groupconsisting of: personal cleansing and/or conditioning agents such ashair care agents such as shampoo agents and/or hair colorant agents,hair conditioning agents, skin care agents, sunscreen agents, and skinconditioning agents; laundry care and/or conditioning agents such asfabric care agents, fabric conditioning agents, fabric softening agents,fabric anti-wrinkling agents, fabric care anti-static agents, fabriccare stain removal agents, soil release agents, dispersing agents, sudssuppressing agents, suds boosting agents, anti-foam agents, and fabricrefreshing agents; liquid and/or powder dishwashing agents (for handdishwashing and/or automatic dishwashing machine applications), hardsurface care agents, and/or conditioning agents and/or polishing agents;other cleaning and/or conditioning agents such as antimicrobial agents,antibacterial agents, antifungal agents, fabric hueing agents, perfume,bleaching agents (such as oxygen bleaching agents, hydrogen peroxide,percarbonate bleaching agents, perborate bleaching agents, chlorinebleaching agents), bleach activating agents, chelating agents, builders,lotions, brightening agents, air care agents, carpet care agents, dyetransfer-inhibiting agents, clay soil removing agents, anti-redepositionagents, polymeric soil release agents, polymeric dispersing agents,alkoxylated polyamine polymers, alkoxylated polycarboxylate polymers,amphilic graft copolymers, dissolution aids, buffering systems,water-softening agents, water-hardening agents, pH adjusting agents,enzymes, flocculating agents, effervescent agents, preservatives,cosmetic agents, make-up removal agents, lathering agents, depositionaid agents, coacervate-forming agents, clays, thickening agents,latexes, silicas, drying agents, odor control agents, antiperspirantagents, cooling agents, warming agents, absorbent gel agents,anti-inflammatory agents, dyes, pigments, acids, and bases; liquidtreatment active agents; agricultural active agents; industrial activeagents; ingestible active agents such as medicinal agents, teethwhitening agents, tooth care agents, mouthwash agents, periodontal gumcare agents, edible agents, dietary agents, vitamins, minerals;water-treatment agents such as water clarifying and/or waterdisinfecting agents, and mixtures thereof.

Non-limiting examples of suitable cosmetic agents, skin care agents,skin conditioning agents, hair care agents, and hair conditioning agentsare described in CTFA Cosmetic Ingredient Handbook, Second Edition, TheCosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992.

One or more classes of chemicals may be useful for one or more of theactive agents listed above. For example, surfactants may be used for anynumber of the active agents described above. Likewise, bleaching agentsmay be used for fabric care, hard surface cleaning, dishwashing and eventeeth whitening. Therefore, one of ordinary skill in the art willappreciate that the active agents will be selected based upon thedesired intended use of the fibrous element and/or particle and/orfibrous structure made therefrom.

For example, if the fibrous element and/or particle and/or fibrousstructure made therefrom is to be used for hair care and/or conditioningthen one or more suitable surfactants, such as a lathering surfactantcould be selected to provide the desired benefit to a consumer whenexposed to conditions of intended use of the fibrous element and/orparticle and/or fibrous structure incorporating the fibrous elementand/or particle.

In one example, if the fibrous element and/or particle and/or fibrousstructure made therefrom is designed or intended to be used forlaundering clothes in a laundry operation, then one or more suitablesurfactants and/or enzymes and/or builders and/or perfumes and/or sudssuppressors and/or bleaching agents could be selected to provide thedesired benefit to a consumer when exposed to conditions of intended useof the fibrous element and/or particle and/or fibrous structureincorporating the fibrous element and/or particle. In another example,if the fibrous element and/or particle and/or fibrous structure madetherefrom is designed to be used for laundering clothes in a laundryoperation and/or cleaning dishes in a dishwashing operation, then thefibrous element and/or particle and/or fibrous structure may comprise alaundry detergent composition or dishwashing detergent composition oractive agents used in such compositions.

In one example, the active agent comprises a non-perfume active agent.In another example, the active agent comprises a non-surfactant activeagent. In still another example, the active agent comprises anon-ingestible active agent, in other words an active agent other thanan ingestible active agent.

Surfactants

Non-limiting examples of suitable surfactants include anionicsurfactants, cationic surfactants, nonionic surfactants, zwitterionicsurfactants, amphoteric surfactants, and mixtures thereof.Co-surfactants may also be included in the fibrous elements and/orparticles. For fibrous elements and/or particles designed for use aslaundry detergents and/or dishwashing detergents, the total level ofsurfactants should be sufficient to provide cleaning including stainand/or odor removal, and generally ranges from about 0.5% to about 95%.Further, surfactant systems comprising two or more surfactants that aredesigned for use in fibrous elements and/or particles for laundrydetergents and/or dishwashing detergents may include all-anionicsurfactant systems, mixed-type surfactant systems comprisinganionic-nonionic surfactant mixtures, or nonionic-cationic surfactantmixtures or low-foaming nonionic surfactants.

The surfactants herein can be linear or branched. In one example,suitable linear surfactants include those derived from agrochemical oilssuch as coconut oil, palm kernel oil, soybean oil, or othervegetable-based oils.

a. Anionic Surfactants

Non-limiting examples of suitable anionic surfactants include alkylsulfates, alkyl ether sulfates, branched alkyl sulfates, branched alkylalkoxylates, branched alkyl alkoxylate sulfates, mid-chain branchedalkyl aryl sulfonates, sulfated monoglycerides, sulfonated olefins,alkyl aryl sulfonates, primary or secondary alkane sulfonates, alkylsulfosuccinates, acyl taurates, acyl isethionates, alkyl glycerylethersulfonate, sulfonated methyl esters, sulfonated fatty acids, alkylphosphates, acyl glutamates, acyl sarcosinates, alkyl sulfoacetates,acylated peptides, alkyl ether carboxylates, acyl lactylates, anionicfluorosurfactants, sodium lauroyl glutamate, and combinations thereof.

Alkyl sulfates and alkyl ether sulfates suitable for use herein includematerials with the respective formula ROSO₃M and RO(C₂H₄O)_(x)SO₃M,wherein R is alkyl or alkenyl of from about 8 to about 24 carbon atoms,x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium,potassium and triethanolamine. Other suitable anionic surfactants aredescribed in McCutcheon's Detergents and Emulsifiers, North AmericanEdition (1986), Allured Publishing Corp. and McCutcheon's, FunctionalMaterials, North American Edition (1992), Allured Publishing Corp.

In one example, anionic surfactants useful in the fibrous elementsand/or particles of the present invention include C₉-C₁₅ alkyl benzenesulfonates (LAS), C₈-C₂₀ alkyl ether sulfates, for example alkylpoly(ethoxy) sulfates, C₈-C₂₀ alkyl sulfates, and mixtures thereof.Other anionic surfactants include methyl ester sulfonates (YMS),secondary alkane sulfonates, methyl ester ethoxylates (MEE), sulfonatedestolides, and mixtures thereof.

In another example, the anionic surfactant is selected from the groupconsisting of: C₁₁-C₁₈ alkyl benzene sulfonates (“LAS”) and primary,branched-chain and random C₁₀-C₂₀ alkyl sulfates (“AS”), C₁₀-C₁₈secondary (2,3) alkyl sulfates of the formula CH₃(CH₂)_(x)(CHOSO₃⁻M⁺)CH₃ and CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺) CH₂CH₃ where x and (y+1) areintegers of at least about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀-C₁₈ alpha-sulfonated fatty acid esters, theC₁₀-C₁₈ sulfated alkyl polyglycosides, the C₁₀-C₁₈ alkyl alkoxy sulfates(“AE_(x)S”) wherein x is from 1-30, and C₁₀-C₁₈ alkyl alkoxycarboxylates, for example comprising 1-5 ethoxy units, mid-chainbranched alkyl sulfates as discussed in U.S. Pat. Nos. 6,020,303 and6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in U.S.Pat. Nos. 6,008,181 and 6,020,303; modified alkylbenzene sulfonate(MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methylester sulfonate (YMS); and alpha-olefin sulfonate (AOS).

b. Cationic Surfactants

Non-limiting examples of suitable cationic surfactants include, but arenot limited to, those having the formula (I):

in which R¹, R², R³, and R⁴ are each independently selected from (a) analiphatic group of from 1 to 26 carbon atoms, or (b) an aromatic,alkoxy, polyoxyalkylene, alkylcarboxy, alkylamido, hydroxyalkyl, aryl oralkylaryl group having up to 22 carbon atoms; and X is a salt-forminganion such as those selected from halogen, (e.g. chloride, bromide),acetate, citrate, lactate, glycolate, phosphate, nitrate, sulphate, andalkylsulphate radicals. In one example, the alkylsulphate radical ismethosulfate and/or ethosulfate.

Suitable quaternary ammonium cationic surfactants of general formula (I)may include cetyltrimethylammonium chloride, behenyltrimethylammoniumchloride (BTAC), stearyltrimethylammonium chloride, cetylpyridiniumchloride, octadecyltrimethylammonium chloride,hexadecyltrimethylammonium chloride, octyldimethylbenzylammoniumchloride, decyldimethylbenzylammonium chloride,stearyldimethylbenzylammonium chloride, didodecyldimethylammoniumchloride, didecyldimehtylammonium chloride, dioctadecyldimethylammoniumchloride, distearyldimethylammonium chloride, tallowtrimethylammoniumchloride, cocotrimethylammonium chloride, 2-ethylhexylstearyldimethylammonumchloride, dipalmitoylethyldimethylammoniumchloride, ditallowoylethyldimethylammonium chloride, distearoylethyldimethylammonium methosulfate, PEG-2 oleylammonium chlorideand salts of these, where the chloride is replaced by halogen, (e.g.,bromide), acetate, citrate, lactate, glycolate, phosphate nitrate,sulphate, or alkylsulphate.

Non-limiting examples of suitable cationic surfactants are commerciallyavailable under the trade names ARQUAD® from Akzo Nobel Surfactants(Chicago, Ill.).

In one example, suitable cationic surfactants include quaternaryammonium surfactants, for example that have up to 26 carbon atomsinclude: alkoxylate quaternary ammonium (AQA) surfactants as discussedin U.S. Pat. No. 6,136,769; dimethyl hydroxyethyl quaternary ammonium asdiscussed in U.S. Pat. No. 6,004,922; dimethyl hydroxyethyl laurylammonium chloride; polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006;cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and 6,022,844; and amino surfactants as discussed inU.S. Pat. No. 6,221,825 and WO 00/47708, for example amidopropyldimethyl amine (APA).

In one example the cationic ester surfactants are hydrolyzable under theconditions of a laundry wash.

c. Nonionic Surfactants

Non-limiting examples of suitable nonionic surfactants includealkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acidamides (PFAA's), alkyl polyglycosides (APG's), C₁₀-C₁₈ glycerol ethers,and the like.

In one example, non-limiting examples of nonionic surfactants useful inthe present invention include: C₁₂-C₁₈ alkyl ethoxylates, such as,NEODOL® nonionic surfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylateswherein the alkoxylate units are a mixture of ethyleneoxy andpropyleneoxy units; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensateswith ethylene oxide/propylene oxide block alkyl polyamine ethoxylatessuch as PLURONIC® from BASF; C₁₄-C₂₂ mid-chain branched alcohols, BA, asdiscussed in U.S. Pat. No. 6,150,322; C₁₄-C₂₂ mid-chain branched alkylalkoxylates, BAE_(x), wherein x is from 1-30, as discussed in U.S. Pat.Nos. 6,153,577, 6,020,303 and 6,093,856; alkylpolysaccharides asdiscussed in U.S. Pat. No. 4,565,647 Llenado, issued Jan. 26, 1986;specifically alkylpolyglycosides as discussed in U.S. Pat. Nos.4,483,780 and 4,483,779; polyhydroxy detergent acid amides as discussedin U.S. Pat. No. 5,332,528; and ether capped poly(oxyalkylated) alcoholsurfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

Examples of commercially available nonionic surfactants suitable for thepresent invention include: Tergitol® 15-S-9 (the condensation product ofC₁₁-C₁₅ linear alcohol with 9 moles ethylene oxide) and Tergitol® 24-L-6NMW (the condensation product of C₁₂-C₁₄ primary alcohol with 6 molesethylene oxide with a narrow molecular weight distribution), bothmarketed by Dow Chemical Company; Neodol® 45-9 (the condensation productof C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol® 23-3(the condensation product of C₁₂-C₁₃ linear alcohol with 3 moles ofethylene oxide), Neodol® 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide) and Neodol® 45-5 (thecondensation product of C₁₄-C₁₅ linear alcohol with 5 moles of ethyleneoxide) marketed by Shell Chemical Company; Kyro® EOB (the condensationproduct of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide), marketed by TheProcter & Gamble Company; and Genapol LA O3O or O5O (the condensationproduct of C₁₂-C₁₄ alcohol with 3 or 5 moles of ethylene oxide) marketedby Clariant. The nonionic surfactants may exhibit an HLB range of fromabout 8 to about 17 and/or from about 8 to about 14. Condensates withpropylene oxide and/or butylene oxides may also be used.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are also suitable for use as a nonionic surfactant in thepresent invention. These compounds include the condensation products ofalkyl phenols having an alkyl group containing from about 6 to about 14carbon atoms, in either a straight-chain or branched-chain configurationwith the alkylene oxide. Commercially available nonionic surfactants ofthis type include Igepal® CO-630, marketed by Solvay-Rhodia; and Triton®X-45, X-114, X-100 and X-102, all marketed by the Dow Chemical Company.

For automatic dishwashing applications, low foaming nonionic surfactantsmay be used. Suitable low foaming nonionic surfactants are disclosed inU.S. Pat. No. 7,271,138 col. 7, line 10 to col. 7, line 60.

Examples of other suitable nonionic surfactants are thecommercially-available Pluronic® surfactants, marketed by BASF, thecommercially available Tetronic® compounds, marketed by BASF, and thecommercially available Plurafac® surfactants, marketed by BASF.

d. Zwitterionic Surfactants

Non-limiting examples of zwitterionic or ampholytic surfactants include:derivatives of secondary and tertiary amines, derivatives ofheterocyclic secondary and tertiary amines, or derivatives of quaternaryammonium, quaternary phosphonium or tertiary sulfonium compounds. SeeU.S. Pat. No. 3,929,678 at column 19, line 38 through column 22, line48, for examples of zwitterionic surfactants; betaines, including alkyldimethyl betaine and cocodimethyl amidopropyl betaine, C₈ to C₁₈ (forexample from C₁₂ to C₁₈) amine oxides and sulfo and hydroxy betaines,such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkylgroup can be C₈ to C₁₈ and in certain embodiments from C₁₀ to C₁₄.

e. Amphoteric Surfactants

Non-limiting examples of amphoteric surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain and mixtures thereof. One ofthe aliphatic substituents may contain at least about 8 carbon atoms,for example from about 8 to about 18 carbon atoms, and at least onecontains an anionic water-solubilizing group, e.g. carboxy, sulfonate,sulfate. See U.S. Pat. No. 3,929,678 at column 19, lines 18-35, forsuitable examples of amphoteric surfactants.

Perfumes

One or more perfume and/or perfume raw materials such as accords and/ornotes may be incorporated into one or more of the fibrous elementsand/or particles of the present invention. The perfume may comprise aperfume ingredient selected from the group consisting of: aldehydeperfume ingredients, ketone perfume ingredients, and mixtures thereof.

One or more perfumes and/or perfumery ingredients may be included in thefibrous elements and/or particles of the present invention. A widevariety of natural and synthetic chemical ingredients useful as perfumesand/or perfumery ingredients include but not limited to aldehydes,ketones, esters, and mixtures thereof. Also included are various naturalextracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. In one example, a finished perfume typically comprisesfrom about 0.01% to about 2% by weight on a dry fibrous element basisand/or a dry particle basis and/or dry fibrous structure basis.

Perfume Delivery Systems

Certain perfume delivery systems, methods of making certain perfumedelivery systems and the uses of such perfume delivery systems aredisclosed in USPA 2007/0275866 A1. Non-limiting examples of perfumedelivery systems include the following:

-   -   I. Polymer Assisted Delivery (PAD): This perfume delivery        technology uses polymeric materials to deliver perfume        materials. Classical coacervation, water soluble or partly        soluble to insoluble charged or neutral polymers, liquid        crystals, hot melts, hydrogels, perfumed plastics,        microcapsules, nano- and micro-latexes, polymeric film formers,        and polymeric absorbents, polymeric adsorbents, etc. are some        examples. PAD includes but is not limited to:

a.) Matrix Systems: The fragrance is dissolved or dispersed in a polymermatrix or particle. Perfumes, for example, may be 1) dispersed into thepolymer prior to formulating into the product or 2) added separatelyfrom the polymer during or after formulation of the product. Diffusionof perfume from the polymer is a common trigger that allows or increasesthe rate of perfume release from a polymeric matrix system that isdeposited or applied to the desired surface (situs), although many othertriggers are know that may control perfume release. Absorption and/oradsorption into or onto polymeric particles, films, solutions, and thelike are aspects of this technology. Nano- or micro-particles composedof organic materials (e.g., latexes) are examples. Suitable particlesinclude a wide range of materials including, but not limited topolyacetal, polyacrylate, polyacrylic, polyacrylonitrile, polyamide,polyaryletherketone, polybutadiene, polybutylene, polybutyleneterephthalate, polychloroprene, polyethylene, polyethyleneterephthalate, polycyclohexylene dimethylene terephthalate,polycarbonate, polychloroprene, polyhydroxyalkanoate, polyketone,polyester, polyethylene, polyetherimide, polyethersulfone,polyethylenechlorinates, polyimide, polyisoprene, polylactic acid,polymethylpentene, polyphenylene oxide, polyphenylene sulfide,polyphthalamide, polypropylene, polystyrene, polysulfone, polyvinylacetate, polyvinyl chloride, as well as polymers or copolymers based onacrylonitrile-butadiene, cellulose acetate, ethylene-vinyl acetate,ethylene vinyl alcohol, styrene-butadiene, vinyl acetate-ethylene, andmixtures thereof.

“Standard” systems refer to those that are “pre-loaded” with the intentof keeping the pre-loaded perfume associated with the polymer until themoment or moments of perfume release. Such polymers may also suppressthe neat product odor and provide a bloom and/or longevity benefitdepending on the rate of perfume release. One challenge with suchsystems is to achieve the ideal balance between 1) in-product stability(keeping perfume inside carrier until you need it) and 2) timely release(during use or from dry situs). Achieving such stability is particularlyimportant during in-product storage and product aging. This challenge isparticularly apparent for aqueous-based, surfactant-containing products,such as heavy duty liquid laundry detergents. Many “Standard” matrixsystems available effectively become “Equilibrium” systems whenformulated into aqueous-based products. One may select an “Equilibrium”system or a Reservoir system, which has acceptable in-product diffusionstability and available triggers for release (e.g., friction).“Equilibrium” systems are those in which the perfume and polymer may beadded separately to the product, and the equilibrium interaction betweenperfume and polymer leads to a benefit at one or more consumer touchpoints (versus a free perfume control that has no polymer-assisteddelivery technology). The polymer may also be pre-loaded with perfume;however, part or all of the perfume may diffuse during in-productstorage reaching an equilibrium that includes having desired perfume rawmaterials (PRMs) associated with the polymer. The polymer then carriesthe perfume to the surface, and release is typically via perfumediffusion. The use of such equilibrium system polymers has the potentialto decrease the neat product odor intensity of the neat product (usuallymore so in the case of pre-loaded standard system). Deposition of suchpolymers may serve to “flatten” the release profile and provideincreased longevity. As indicated above, such longevity would beachieved by suppressing the initial intensity and may enable theformulator to use more high impact or low odor detection threshold (ODT)or low Kovats Index (KI) PRMs to achieve initial product odor benefitswithout initial intensity that is too strong or distorted. It isimportant that perfume release occurs within the time frame of theapplication to impact the desired consumer touch point or touch points.Suitable micro-particles and micro-latexes as well as methods of makingsame may be found in USPA 2005/0003980 A1. Matrix systems also includehot melt adhesives and perfume plastics. In addition, hydrophobicallymodified polysaccharides may be formulated into the perfumed product toincrease perfume deposition and/or modify perfume release. All suchmatrix systems, including for example polysaccharides and nanolatexesmay be combined with other PDTs, including other PAD systems such as PADreservoir systems in the form of a perfume microcapsule (PMC). PolymerAssisted Delivery (PAD) matrix systems may include those described inthe following references: US Patent Applications 2004/0110648 A1;2004/0092414 A1; 2004/0091445 A1 and 2004/0087476 A1; and U.S. Pat. Nos.6,531,444; 6,024,943; 6,042,792; 6,051,540; 4,540,721 and 4,973,422.

Silicones are also examples of polymers that may be used as PDT, and canprovide perfume benefits in a manner similar to the polymer-assisteddelivery “matrix system”. Such a PDT is referred to as silicone-assisteddelivery (SAD). One may pre-load silicones with perfume, or use them asan equilibrium system as described for PAD. Suitable silicones as wellas making same may be found in WO 2005/102261; USPA 20050124530A1; USPA20050143282A1; and WO 2003/015736. Functionalized silicones may also beused as described in USPA 2006/003913 A1. Examples of silicones includepolydimethylsiloxane and polyalkyldimethylsiloxanes. Other examplesinclude those with amine functionality, which may be used to providebenefits associated with amine-assisted delivery (AAD) and/orpolymer-assisted delivery (PAD) and/or amine-reaction products (ARP).Other such examples may be found in U.S. Pat. No. 4,911,852; USPA2004/0058845 A1; USPA 2004/0092425 A1 and USPA 2005/0003980 A1.

b.) Reservoir Systems: Reservoir systems are also known as a core-shelltype technology, or one in which the fragrance is surrounded by aperfume release controlling membrane, which may serve as a protectiveshell. The material inside the microcapsule is referred to as the core,internal phase, or fill, whereas the wall is sometimes called a shell,coating, or membrane. Microparticles or pressure sensitive capsules ormicrocapsules are examples of this technology. Microcapsules of thecurrent invention are formed by a variety of procedures that include,but are not limited to, coating, extrusion, spray-drying, interfacial,in-situ and matrix polymerization. The possible shell materials varywidely in their stability toward water. Among the most stable arepolyoxymethyleneurea (PMU)-based materials, which may hold certain PRMsfor even long periods of time in aqueous solution (or product). Suchsystems include but are not limited to urea-formaldehyde and/ormelamine-formaldehyde. Stable shell materials include polyacrylate-basedmaterials obtained as reaction product of an oil soluble or dispersibleamine with a multifunctional acrylate or methacrylate monomer oroligomer, an oil soluble acid and an initiator, in presence of ananionic emulsifier comprising a water soluble or water dispersibleacrylic acid alkyl acid copolymer, an alkali or alkali salt.Gelatin-based microcapsules may be prepared so that they dissolvequickly or slowly in water, depending for example on the degree ofcross-linking. Many other capsule wall materials are available and varyin the degree of perfume diffusion stability observed. Without wishingto be bound by theory, the rate of release of perfume from a capsule,for example, once deposited on a surface is typically in reverse orderof in-product perfume diffusion stability. As such, urea-formaldehydeand melamine-formaldehyde microcapsules for example, typically require arelease mechanism other than, or in addition to, diffusion for release,such as mechanical force (e.g., friction, pressure, shear stress) thatserves to break the capsule and increase the rate of perfume (fragrance)release. Other triggers include melting, dissolution, hydrolysis orother chemical reaction, electromagnetic radiation, and the like. Theuse of pre-loaded microcapsules requires the proper ratio of in-productstability and in-use and/or on-surface (on-situs) release, as well asproper selection of PRMs. Microcapsules that are based onurea-formaldehyde and/or melamine-formaldehyde are relatively stable,especially in near neutral aqueous-based solutions. These materials mayrequire a friction trigger which may not be applicable to all productapplications. Other microcapsule materials (e.g., gelatin) may beunstable in aqueous-based products and may even provide reduced benefit(versus free perfume control) when in-product aged. Scratch and snifftechnologies are yet another example of PAD. Perfume microcapsules (PMC)may include those described in the following references: US PatentApplications: 2003/0125222 A1; 2003/215417 A1; 2003/216488 A1;2003/158344 A1; 2003/165692 A1; 2004/071742 A1; 2004/071746 A1;2004/072719 A1; 2004/072720 A1; 2006/0039934 A1; 2003/203829 A1;2003/195133 A1; 2004/087477 A1; 2004/0106536 A1; and U.S. Pat. Nos.6,645,479 B1; 6,200,949 B1; 4,882,220; 4,917,920; 4,514,461; 6,106,875and 4,234,627, 3,594,328 and US RE 32713, PCT Patent Application: WO2009/134234 A1, WO 2006/127454 A2, WO 2010/079466 A2, WO 2010/079467 A2,WO 2010/079468 A2, WO 2010/084480 A2.

-   -   II. Molecule-Assisted Delivery (MAD): Non-polymer materials or        molecules may also serve to improve the delivery of perfume.        Without wishing to be bound by theory, perfume may        non-covalently interact with organic materials, resulting in        altered deposition and/or release. Non-limiting examples of such        organic materials include but are not limited to hydrophobic        materials such as organic oils, waxes, mineral oils, petrolatum,        fatty acids or esters, sugars, surfactants, liposomes and even        other perfume raw material (perfume oils), as well as natural        oils, including body and/or other soils. Perfume fixatives are        yet another example. In one aspect, non-polymeric materials or        molecules have a C Log P greater than about 2. Molecule-Assisted        Delivery (MAD) may also include those described in U.S. Pat.        Nos. 7,119,060 and 5,506,201.    -   III. Fiber-Assisted Delivery (FAD): The choice or use of a situs        itself may serve to improve the delivery of perfume. In fact,        the situs itself may be a perfume delivery technology. For        example, different fabric types such as cotton or polyester will        have different properties with respect to ability to attract        and/or retain and/or release perfume. The amount of perfume        deposited on or in fibers may be altered by the choice of fiber,        and also by the history or treatment of the fiber, as well as by        any fiber coatings or treatments. Fibers may be woven and        non-woven as well as natural or synthetic. Natural fibers        include those produced by plants, animals, and geological        processes, and include but are not limited to cellulose        materials such as cotton, linen, hemp jute, flax, ramie, and        sisal, and fibers used to manufacture paper and cloth.        Fiber-Assisted Delivery may consist of the use of wood fiber,        such as thermomechanical pulp and bleached or unbleached kraft        or sulfite pulps. Animal fibers consist largely of particular        proteins, such as silk, feathers, sinew, catgut and hair        (including wool). Polymer fibers based on synthetic chemicals        include but are not limited to polyamide nylon, PET or PBT        polyester, phenol-formaldehyde (PF), polyvinyl alcohol fiber        (PVOH), polyvinyl chloride fiber (PVC), polyolefins (PP and PE),        and acrylic polymers. All such fibers may be pre-loaded with a        perfume, and then added to a product that may or may not contain        free perfume and/or one or more perfume delivery technologies.        In one aspect, the fibers may be added to a product prior to        being loaded with a perfume, and then loaded with a perfume by        adding a perfume that may diffuse into the fiber, to the        product. Without wishing to be bound by theory, the perfume may        absorb onto or be adsorbed into the fiber, for example, during        product storage, and then be released at one or more moments of        truth or consumer touch points.    -   IV. Amine Assisted Delivery (AAD): The amine-assisted delivery        technology approach utilizes materials that contain an amine        group to increase perfume deposition or modify perfume release        during product use. There is no requirement in this approach to        pre-complex or pre-react the perfume raw material(s) and amine        prior to addition to the product. In one aspect,        amine-containing AAD materials suitable for use herein may be        non-aromatic; for example, polyalkylimine, such as        polyethyleneimine (PEI), or polyvinylamine (PVAm), or aromatic,        for example, anthranilates. Such materials may also be polymeric        or non-polymeric. In one aspect, such materials contain at least        one primary amine. This technology will allow increased        longevity and controlled release also of low ODT perfume notes        (e.g., aldehydes, ketones, enones) via amine functionality, and        delivery of other PRMs, without being bound by theory, via        polymer-assisted delivery for polymeric amines. Without        technology, volatile top notes can be lost too quickly, leaving        a higher ratio of middle and base notes to top notes. The use of        a polymeric amine allows higher levels of top notes and other        PRMS to be used to obtain freshness longevity without causing        neat product odor to be more intense than desired, or allows top        notes and other PRMs to be used more efficiently. In one aspect,        AAD systems are effective at delivering PRMs at pH greater than        about neutral. Without wishing to be bound by theory, conditions        in which more of the amines of the AAD system are deprotonated        may result in an increased affinity of the deprotonated amines        for PRMs such as aldehydes and ketones, including unsaturated        ketones and enones such as damascone. In another aspect,        polymeric amines are effective at delivering PRMs at pH less        than about neutral. Without wishing to be bound by theory,        conditions in which more of the amines of the AAD system are        protonated may result in a decreased affinity of the protonated        amines for PRMs such as aldehydes and ketones, and a strong        affinity of the polymer framework for a broad range of PRMs. In        such an aspect, polymer-assisted delivery may be delivering more        of the perfume benefit; such systems are a subspecies of AAD and        may be referred to as Amine-Polymer-Assisted Delivery or APAD.        In some cases when the APAD is employed in a composition that        has a pH of less than seven, such APAD systems may also be        considered Polymer-Assisted Delivery (PAD). In yet another        aspect, AAD and PAD systems may interact with other materials,        such as anionic surfactants or polymers to form coacervate        and/or coacervates-like systems. In another aspect, a material        that contains a heteroatom other than nitrogen, for example        sulfur, phosphorus or selenium, may be used as an alternative to        amine compounds. In yet another aspect, the aforementioned        alternative compounds can be used in combination with amine        compounds. In yet another aspect, a single molecule may comprise        an amine moiety and one or more of the alternative heteroatom        moieties, for example, thiols, phosphines and selenols. Suitable        AAD systems as well as methods of making same may be found in US        Patent Applications 2005/0003980 A1; 2003/0199422 A1;        2003/0036489 A1; 2004/0220074 A1 and U.S. Pat. No. 6,103,678.    -   V. Cyclodextrin Delivery System (CD): This technology approach        uses a cyclic oligosaccharide or cyclodextrin to improve the        delivery of perfume. Typically a perfume and cyclodextrin (CD)        complex is formed. Such complexes may be preformed, formed        in-situ, or formed on or in the situs. Without wishing to be        bound by theory, loss of water may serve to shift the        equilibrium toward the CD-Perfume complex, especially if other        adjunct ingredients (e.g., surfactant) are not present at high        concentration to compete with the perfume for the cyclodextrin        cavity. A bloom benefit may be achieved if water exposure or an        increase in moisture content occurs at a later time point. In        addition, cyclodextrin allows the perfume formulator increased        flexibility in selection of PRMs. Cyclodextrin may be pre-loaded        with perfume or added separately from perfume to obtain the        desired perfume stability, deposition or release benefit.        Suitable CDs as well as methods of making same may be found in        USPA 2005/0003980 A1 and 2006/0263313 A1 and U.S. Pat. Nos.        5,552,378; 3,812,011; 4,317,881; 4,418,144 and 4,378,923.    -   VI. Starch Encapsulated Accord (SEA): The use of a starch        encapsulated accord (SEA) technology allows one to modify the        properties of the perfume, for example, by converting a liquid        perfume into a solid by adding ingredients such as starch. The        benefit includes increased perfume retention during product        storage, especially under non-aqueous conditions. Upon exposure        to moisture, a perfume bloom may be triggered. Benefits at other        moments of truth may also be achieved because the starch allows        the product formulator to select PRMs or PRM concentrations that        normally cannot be used without the presence of SEA. Another        technology example includes the use of other organic and        inorganic materials, such as silica to convert perfume from        liquid to solid. Suitable SEAs as well as methods of making same        may be found in USPA 2005/0003980 A1 and U.S. Pat. No. 6,458,754        B1.    -   VII. Inorganic Carrier Delivery System (ZIC): This technology        relates to the use of porous zeolites or other inorganic        materials to deliver perfumes. Perfume-loaded zeolite may be        used with or without adjunct ingredients used for example to        coat the perfume-loaded zeolite (PLZ) to change its perfume        release properties during product storage or during use or from        the dry situs. Suitable zeolite and inorganic carriers as well        as methods of making same may be found in USPA 2005/0003980 A1        and U.S. Pat. Nos. 5,858,959; 6,245,732 B1; 6,048,830 and        4,539,135. Silica is another form of ZIC. Another example of a        suitable inorganic carrier includes inorganic tubules, where the        perfume or other active material is contained within the lumen        of the nano- or micro-tubules. In one aspect, the perfume-loaded        inorganic tubule (or Perfume-Loaded Tubule or PLT) is a mineral        nano- or micro-tubule, such as halloysite or mixtures of        halloysite with other inorganic materials, including other        clays. The PLT technology may also comprise additional        ingredients on the inside and/or outside of the tubule for the        purpose of improving in-product diffusion stability, deposition        on the desired situs or for controlling the release rate of the        loaded perfume. Monomeric and/or polymeric materials, including        starch encapsulation, may be used to coat, plug, cap, or        otherwise encapsulate the PLT. Suitable PLT systems as well as        methods of making same may be found in U.S. Pat. No. 5,651,976.    -   VIII. Pro-Perfume (PP): This technology refers to perfume        technologies that result from the reaction of perfume materials        with other substrates or chemicals to form materials that have a        covalent bond between one or more PRMs and one or more carriers.        The PRM is converted into a new material called a pro-PRM (i.e.,        pro-perfume), which then may release the original PRM upon        exposure to a trigger such as water or light. Pro-perfumes may        provide enhanced perfume delivery properties such as increased        perfume deposition, longevity, stability, retention, and the        like. Pro-perfumes include those that are monomeric        (non-polymeric) or polymeric, and may be pre-formed or may be        formed in-situ under equilibrium conditions, such as those that        may be present during in-product storage or on the wet or dry        situs. Nonlimiting examples of pro-perfumes include Michael        adducts (e.g., beta-amino ketones), aromatic or non-aromatic        imines (Schiff bases), oxazolidines, beta-keto esters, and        orthoesters. Another aspect includes compounds comprising one or        more beta-oxy or beta-thio carbonyl moieties capable of        releasing a PRM, for example, an alpha, beta-unsaturated ketone,        aldehyde or carboxylic ester. The typical trigger for perfume        release is exposure to water; although other triggers may        include enzymes, heat, light, pH change, autoxidation, a shift        of equilibrium, change in concentration or ionic strength and        others. For aqueous-based products, light-triggered pro-perfumes        are particularly suited. Such photo-pro-perfumes (PPPs) include        but are not limited to those that release coumarin derivatives        and perfumes and/or pro-perfumes upon being triggered. The        released pro-perfume may release one or more PRMs by means of        any of the above mentioned triggers. In one aspect, the        photo-pro-perfume releases a nitrogen-based pro-perfume when        exposed to a light and/or moisture trigger. In another aspect,        the nitrogen-based pro-perfume, released from the        photo-pro-perfume, releases one or more PRMs selected, for        example, from aldehydes, ketones (including enones) and        alcohols. In still another aspect, the PPP releases a dihydroxy        coumarin derivative. The light-triggered pro-perfume may also be        an ester that releases a coumarin derivative and a perfume        alcohol. In one aspect the pro-perfume is a dimethoxybenzoin        derivative as described in USPA 2006/0020459 A1. In another        aspect the pro-perfume is a 3′,5′-dimethoxybenzoin (DMB)        derivative that releases an alcohol upon exposure to        electromagnetic radiation. In yet another aspect, the        pro-perfume releases one or more low ODT PRMs, including        tertiary alcohols such as linalool, tetrahydrolinalool, or        dihydromyrcenol. Suitable pro-perfumes and methods of making        same can be found in U.S. Pat. Nos. 7,018,978 B2; 6,987,084 B2;        6,956,013 B2; 6,861,402 B1; 6,544,945 B1; 6,093,691; 6,277,796        B1; 6,165,953; 6,316,397 B1; 6,437,150 B1; 6,479,682 B1;        6,096,918; 6,218,355 B1; 6,133,228; 6,147,037; 7,109,153 B2;        7,071,151 B2; 6,987,084 B2; 6,610,646 B2 and 5,958,870, as well        as can be found in USPA 2005/0003980 A1 and USPA 2006/0223726        A1.

a.) Amine Reaction Product (ARP): For purposes of the presentapplication, ARP is a subclass or species of PP. One may also use“reactive” polymeric amines in which the amine functionality ispre-reacted with one or more PRMs to form an amine reaction product(ARP). Typically the reactive amines are primary and/or secondaryamines, and may be part of a polymer or a monomer (non-polymer). SuchARPs may also be mixed with additional PRMs to provide benefits ofpolymer-assisted delivery and/or amine-assisted delivery. Nonlimitingexamples of polymeric amines include polymers based on polyalkylimines,such as polyethyleneimine (PEI), or polyvinylamine (PVAm). Nonlimitingexamples of monomeric (non-polymeric) amines include hydroxyl amines,such as 2-aminoethanol and its alkyl substituted derivatives, andaromatic amines such as anthranilates. The ARPs may be premixed withperfume or added separately in leave-on or rinse-off applications. Inanother aspect, a material that contains a heteroatom other thannitrogen, for example oxygen, sulfur, phosphorus or selenium, may beused as an alternative to amine compounds. In yet another aspect, theaforementioned alternative compounds can be used in combination withamine compounds. In yet another aspect, a single molecule may comprisean amine moiety and one or more of the alternative heteroatom moieties,for example, thiols, phosphines and selenols. The benefit may includeimproved delivery of perfume as well as controlled perfume release.Suitable ARPs as well as methods of making same can be found in USPA2005/0003980 A1 and U.S. Pat. No. 6,413,920 B1.

Antimicrobials, Antibacterials & Antifungals

In an embodiment, pyridinethione particulates are suitable antimicrobialactive agents for use in the present invention. In an embodiment, theantimicrobial active agent is a 1-hydroxy-2-pyridinethione salt and isin particulate form. In an embodiment, the concentration ofpyridinethione particulate ranges from about 0.01 wt % to about 5 wt %,or from about 0.1 wt % to about 3 wt %, or from about 0.1 wt % to about2 wt %, by weight of the dry fibrous element and/or dry particle and/ordry fibrous structure of the present invention. In an embodiment, thepyridinethione salts are those formed from heavy metals such as zinc,tin, cadmium, magnesium, aluminium and zirconium, generally zinc,typically the zinc salt of 1-hydroxy-2-pyridinethione (known as “zincpyridinethione” or “ZPT”), commonly 1-hydroxy-2-pyridinethione salts inplatelet particle form. In an embodiment, the 1-hydroxy-2-pyridinethionesalts in platelet particle form have an average particle size of up toabout 20 microns, or up to about 5 microns, or up to about 2.5 micronsas measured according to the Median Particle Size Test Method describedherein. Salts formed from other cations, such as sodium, may also besuitable. Pyridinethione actives are described, for example, in U.S.Pat. Nos. 2,809,971; 3,236,733; 3,753,196; 3,761,418; 4,345,080;4,323,683; 4,379,753; and 4,470,982.

In another embodiment, the antibacterial is chosen from triclosan,triclocarban, chlorohexidine, metronitazole and mixtures thereof.

In an embodiment, in addition to the antimicrobial active selected frompolyvalent metal salts of pyrithione, the composition can furtherinclude one or more anti-fungal and/or anti-microbial actives. In anembodiment, the anti-microbial active is selected from the groupconsisting of: coal tar, sulfur, azoles, selenium sulphide, particulatesulphur, keratolytic agents, charcoal, whitfield's ointment,castellani's paint, aluminum chloride, gentian violet, octopirox(piroctone olamine), ciclopirox olamine, undecylenic acid and its metalsalts, potassium permanganate, selenium sulphide, sodium thiosulfate,propylene glycol, oil of bitter orange, urea preparations, griseofulvin,8-hydroxyquinoline ciloquinol, thiobendazole, thiocarbamates,haloprogin, polyenes, hydroxypyridone, morpholine, benzylamine,allylamines (such as terbinafine), tea tree oil, clove leaf oil,coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamicaldehyde, citronellic acid, hinokitol, ichthyol pale, Sensiva SC-50,Elestab HP-100, azelaic acid, lyticase, iodopropynyl butylcarbamate(IPBC), isothiazalinones such as octyl isothiazalinone, and azoles, andmixtures thereof.

Bleaching Agents

The fibrous elements and/or particles of the present invention maycomprise one or more bleaching agents. Non-limiting examples of suitablebleaching agents include peroxyacids, perborate, percarbonate, chlorinebleaches, oxygen bleaches, hypohalite bleaches, bleach precursors,bleach activators, bleach catalysts, hydrogen peroxide, bleach boosters,photobleaches, bleaching enzymes, free radical initiators, peroxygenbleaches, and mixtures thereof.

One or more bleaching agents may be included in the fibrous elementsand/or particles of the present invention may be included at a levelfrom about 0.05% to about 30% and/or from about 1% to about 20% byweight on a dry fibrous element basis and/or dry particle basis and/ordry fibrous structure basis. If present, bleach activators may bepresent in the fibrous elements and/or particles of the presentinvention at a level from about 0.1% to about 60% and/or from about 0.5%to about 40% by weight on a dry fibrous element basis and/or dryparticle basis and/or dry fibrous structure basis.

Non-limiting examples of bleaching agents include oxygen bleach,perborate bleach, percarboxylic acid bleach and salts thereof, peroxygenbleach, persulfate bleach, percarbonate bleach, and mixtures thereof.Further, non-limiting examples of bleaching agents are disclosed in U.S.Pat. No. 4,483,781, European Patent Application 0 133 354, U.S. Pat.Nos. 4,412,934, and 4,634,551.

Non-limiting examples of bleach activators (e.g., acyl lactamactivators) are disclosed in U.S. Pat. Nos. 4,915,854; 4,412,934;4,634,551; and 4,966,723.

In one example, the bleaching agent comprises a transition metal bleachcatalyst, which may be encapsulated. The transition metal bleachcatalyst typically comprises a transition metal ion, for example atransition metal ion from a transition metal selected from the groupconsisting of: Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV),Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV).In one example, the transition metal is selected from the groupconsisting of: Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Cr(II),Cr(III), Cr(IV), Cr(V), and Cr(VI). The transition metal bleach catalysttypically comprises a ligand, for example a macropolycyclic ligand, suchas a cross-bridged macropolycyclic ligand. The transition metal ion maybe coordinated with the ligand. Further, the ligand may comprise atleast four donor atoms, at least two of which are bridgehead donoratoms. Non-limiting examples of suitable transition metal bleachcatalysts are described in U.S. Pat. Nos. 5,580,485, 4,430,243;4,728,455; 5,246,621; 5,244,594; 5,284,944; 5,194,416; 5,246,612;5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084; 5,114,606;5,114,611, EP 549,271 A1; EP 544,490 A1; EP 549,272 A1; and EP 544,440A2. In one example, a suitable transition metal bleach catalystcomprises a manganese-based catalyst, for example disclosed in U.S.5,576,282. In another example, suitable cobalt bleach catalysts aredescribed, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967. In yet another,suitable transition metal bleach catalysts comprise a transition metalcomplex of ligand such as bispidones described in WO 05/042532 A1.

Non-limiting examples of bleach catalysts include a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243. Other types ofbleach catalysts include the manganese-based complexes disclosed in U.S.Pat. Nos. 5,246,621 and 5,244,594. Preferred examples of thesescatalysts include Mn.sup.IV.sub.2 (u-O).sub.3(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2-(PF.sub.6).sub.2(“MnTACN”), Mn.sup.III.sub.2 (u-O).sub.1 (u-OAc).sub.2(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2-(ClO.sub.4).sub.2,Mn.sup.IV.sub.4 (u-O).sub.6(1,4,7-triazacyclononane).sub.4-(ClO.sub.4).sub.2, Mn. sup.III Mn.sup.IV.sub.4 (u-O).sub.1 (u-OAc).sub.2(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2-(ClO.sub.4).sub.3, andmixtures thereof. See also European patent application publication no.549,272. Other ligands suitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, andmixtures thereof. The bleach catalysts useful in automatic dishwashingcompositions and concentrated powder detergent compositions may also beselected as appropriate for the present invention. For examples ofsuitable bleach catalysts see U.S. Pat. Nos. 4,246,612 and 5,227,084.See also U.S. Pat. No. 5,194,416 which teaches mononuclear manganese(IV) complexes such asMn(1,4,7-trimethyl-1,4,7-triazacyclononane(OCH3).sub.3-(PF.sub.6). Stillanother type of bleach catalyst, as disclosed in U.S. Pat. No.5,114,606, is a water-soluble complex of manganese (II), (III), and/or(UV) with a ligand which is a non-carboxylate polyhydroxy compoundhaving at least three consecutive C—OH groups. Preferred ligands includesorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol,meso-erythritol, meso-inositol, lactose, and mixtures thereof. U.S. Pat.No. 5,114,611 teaches a bleach catalyst comprising a complex oftransition metals, including Mn, Co, Fe, or Cu, with annon-(macro)-cyclic ligand. Non-limiting examples of ligands includepyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, andtriazole rings. In one example, the ligand is 2,2′-bispyridylamine. Inone example, the bleach catalysts includes a Co, Cu, Mn,Fe,-bispyridylmethane and -bispyridylamine complex, such asCo(2,2′-bispyridylamine)Cl₂, Di(isothiocyanato) bispyridylamine-cobalt(II), trisdipyridylamine-cobalt(II) perchlorate,Co(2,2-bispyridylamine)₂O₂ClO₄, Bis-(2,2′-bispyridylamine) copper(II)perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixturesthereof. Other examples of bleach catalysts include Mn gluconate,Mn(CF₃SO₃)₂, Co(NH₃)₅CI, and the binuclear Mn complexed withtetra-N-dentate and bi-N-dentate ligands, including N₄Mn(III) (u-O)₂Mn(IV) N₄)⁺ and [Bipy₂Mn(III) (u-O)₂Mn(IV) bipy₂]-(ClO₄)₃.

The bleach catalysts may also be prepared by combining a water-solubleligand with a water-soluble manganese salt in aqueous media andconcentrating the resulting mixture by evaporation. Any convenientwater-soluble salt of manganese can be used herein. Manganese (II),(III), (IV) and/or (V) is readily available on a commercial scale. Insome instances, sufficient manganese may be present in the wash liquor,but, in general, it is preferred to detergent composition Mn cations inthe compositions to ensure its presence in catalytically-effectiveamounts. Thus, the sodium salt of the ligand and a member selected fromthe group consisting of MnSO.sub.4, Mn(ClO.sub.4).sub.2 or MnCl.sub.2(least preferred) are dissolved in water at molar ratios of ligand:Mnsalt in the range of about 1:4 to 4:1 at neutral or slightly alkalinepH. The water may first be de-oxygenated by boiling and cooled byspraying with nitrogen. The resulting solution is evaporated (underN.sub.2, if desired) and the resulting solids are used in the bleachingand detergent compositions herein without further purification.

In an alternate mode, the water-soluble manganese source, such asMnSO.sub.4, is added to the bleach/cleaning composition or to theaqueous bleaching/cleaning bath which comprises the ligand. Some type ofcomplex is apparently formed in situ, and improved bleach performance issecured. In such an in situ process, it is convenient to use aconsiderable molar excess of the ligand over the manganese, and moleratios of ligand:Mn typically are 3:1 to 15:1. The additional ligandalso serves to scavenge vagrant metal ions such as iron and copper,thereby protecting the bleach from decomposition. One possible suchsystem is described in European patent application, publication no. 549,271.

While the structures of the bleach-catalyzing manganese complexes usefulin the present invention have not been elucidated, it may be speculatedthat they comprise chelates or other hydrated coordination complexeswhich result from the interaction of the carboxyl and nitrogen atoms ofthe ligand with the manganese cation. Likewise, the oxidation state ofthe manganese cation during the catalytic process is not known withcertainty, and may be the (+II), (+III), (+IV) or (+V) valence state.Due to the ligands' possible six points of attachment to the manganesecation, it may be reasonably speculated that multi-nuclear speciesand/or “cage” structures may exist in the aqueous bleaching media.Whatever the form of the active Mnâ

¢ligand species which actually exists, it functions in an apparentlycatalytic manner to provide improved bleaching performances on stubbornstains such as tea, ketchup, coffee, wine, juice, and the like.

Other bleach catalysts are described, for example, in European patentapplication, publication no. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEuropean patent application, publication no. 224,952, (absorbedmanganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845(aluminosilicate support with manganese and zinc or magnesium salt),U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No.4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019(cobalt chelant catalyst) Canadian 866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

In one example, the bleach catalyst comprises a cobalt pentaaminechloride salts having the formula [Co(NH.sub.3).sub.5 Cl] Y.sub.y, andespecially [Co(NH.sub.3).sub.5 Cl]CI.sub.2. Other cobalt bleachcatalysts useful herein are described for example along with their basehydrolysis rates, in M. L. Tobe, “Base Hydrolysis of Transition-MetalComplexes”, Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. Forexample, Table 1 at page 17, provides the base hydrolysis rates(designated therein as k.sub.OH) for cobalt pentaamine catalystscomplexed with oxalate (k.sub.OH=2.5Ã-10.sup.-4 M.sup.-1 s.sup.−1 (25Â°C.)), NCS.sup.-(.sub.OH=5.0Ã-10.sup.-4 M. sup.-1 s.sup.-1 (25Â° C.)),formate (k.sub.OH=5.8. times.10.sup.-4 M.sup.-1 s.sup.-1 (25Â° C.)), andacetate (k.sub.OH=9.6Ã-10. sup.-4 M.sup.-1 s.sup.-1 (25Â° C.)). The mostpreferred cobalt catalyst useful herein are cobalt pentaamine acetatesalts having the formula [Co(NH.sub.3).sub.5 OAc]T.sub.y, wherein OAcrepresents an acetate moiety, and especially cobalt pentaamine acetatechloride, [Co(NH.sub.3).sub.5 OAc]Cl.sub.2; as well as[Co(NH.sub.3).sub.5 OAc](OAc).sub.2; [Co(NH.sub.3).sub.5OAc](PF.sub.6).sub.2; [Co(NH.sub.3).sub.5 OAc] (SO.sub.4);[Co(NH.sub.3).sub.5 OAc] (BF.sub.4).sub.2; and [Co(NH.sub.3).sub.5 OAc](NO.sub.3).sub.2.

These bleach catalysts may be readily prepared by known procedures, suchas taught for example in the Tobe article hereinbefore and thereferences cited therein, in U.S. Pat. No. 4,810,410, to Diakun et al,issued Mar. 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; TheSynthesis and Characterization of Inorganic Compounds, W. L. Jolly(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979);Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979);Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry 56,22-25 (1952). These bleach catalysts may also be coprocessed withadjunct materials so as to reduce the color impact if desired for theaesthetics of the product, or to be included in enzyme-containingparticles as exemplified hereinafter, or the compositions may bemanufactured to contain catalyst “speckles”.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein (e.g., photoactivated bleachingagents such as the sulfonated zinc and/or aluminum phthalocyanines (U.S.Pat. No. 4,033,718, incorporated herein by reference)), and/orpre-formed organic peracids, such as peroxycarboxylic acid or saltthereof, and/or peroxysulphonic acids or salts thereof. In one example,a suitable organic peracid comprises phthaloylimidoperoxycaproic acid orsalt thereof. When present, the photoactivated bleaching agents, such assulfonated zinc phthalocyanine, may be present in the fibrous elementsand/or particles and/or fibrous structures of the present invention at alevel from about 0.025% to about 1.25% by weight on a dry fibrouselement basis and/or dry particle basis and/or dry fibrous structurebasis.

Non-limiting examples of bleach activators are selected from the groupconsisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam(BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoyl-caprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzene-sulphonate(NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate(C.sub.10-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate(C.sub.8-OBS), perhydrolyzable esters and mixtures thereof, mostpreferably benzoylcaprolactam and benzoylvalerolactam. Particularlypreferred bleach activators in the pH range from about 8 to about 9.5are those selected having an OBS or VL leaving group. Quaternarysubstituted bleach activators (a quaternary substituted bleach activator(QSBA) or a quaternary substituted peracid (QSP)) may also be included.

Non-limiting examples of organic peroxides, such as diacyl peroxides areextensively illustrated in Kirk Othmer, Encyclopedia of ChemicalTechnology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 andespecially at pages 63-72, all incorporated wherein by reference. If adiacyl peroxide is used, it may be one which exerts minimal adverseimpact on spotting/filming.

Dye Transfer Inhibiting Agents

The fibrous elements and/or particles of the present invention mayinclude one or more dye transfer inhibiting agents. Suitable polymericdye transfer inhibiting agents include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. The dye transfer inhibitingagents may be present in the fibrous elements and/or particles and/orfibrous structure products of the present invention at levels from about0.0001% to about 10%, from about 0.01% to about 5% or even from about0.1% to about 3% by weight on a dry fibrous element basis and/or dryparticle basis and/or dry fibrous structure basis.

Brighteners

The fibrous elements and/or particles of the present invention maycontain active agents, such as brighteners, for example fluorescentbrighteners. Such brighteners may tint articles being cleaned.

The fibrous elements and/or particles may comprise C.I. fluorescentbrightener 260 in α-crystalline form having the following structure:

In one aspect, the brightener is a cold water-soluble brightener, suchas the C.I. fluorescent brightener 260 in α-crystalline form.

In one aspect the brightener is predominantly in α-crystalline form,which means that typically at least 50 wt %, at least 75 wt %, at least90 wt %, at least 99 wt %, or even substantially all, of the C.I.fluorescent brightener 260 is in α-crystalline form.

The brightener is typically in a micronized particulate form, having aweight average primary particle size of from 3 to 30 μm, from 3 to 20μm, or from 3 to 10 μm as measured according to the Median Particle SizeTest Method

The composition may comprises C.I. fluorescent brightener 260 inβ-crystalline form, and the weight ratio of: (i) C.I. fluorescentbrightener 260 in α-crystalline form, to (ii) C.I. fluorescentbrightener 260 in β-crystalline form may be at least 0.1, or at least0.6.

BE680847 relates to a process for making C.I fluorescent brightener 260in α-crystalline form.

Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, coumarin,carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.Examples of such brighteners are disclosed in “The Production andApplication of Fluorescent Brightening Agents”, M. Zahradnik, Publishedby John Wiley & Sons, New York (1982). Specific nonlimiting examples ofoptical brighteners which are useful in the present compositions arethose identified in U.S. Pat. Nos. 4,790,856 and 3,646,015.

A further suitable brightener has the structure below:

Suitable fluorescent brightener levels include lower levels of fromabout 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt %to upper levels of 0.5 or even 0.75 wt %.

In one aspect the brightener may be loaded onto a clay to form aparticle.

Hueing Agents

The composition may comprise a hueing agent. Suitable hueing agentsinclude dyes, dye-clay conjugates, and pigments. Suitable dyes includesmall molecule dyes and polymeric dyes. Suitable small molecule dyesinclude small molecule dyes selected from the group consisting of dyesfalling into the Colour Index (C.I.) classifications of Direct Blue,Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue,Basic Violet and Basic Red, or mixtures thereof.

In another aspect, suitable small molecule dyes include small moleculedyes selected from the group consisting of Colour Index (Society ofDyers and Colourists, Bradford, UK) numbers Direct Violet 9, DirectViolet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, DirectViolet 99, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, AcidViolet 49, Acid Violet 50, Acid Blue 15, Acid Blue 17, Acid Blue 25,Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80,Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35,Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue66, Basic Blue 75, Basic Blue 159 and mixtures thereof. In anotheraspect, suitable small molecule dyes include small molecule dyesselected from the group consisting of Colour Index (Society of Dyers andColourists, Bradford, UK) numbers Acid Violet 17, Acid Violet 43, AcidRed 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, DirectBlue 71, Direct Violet 51 and mixtures thereof. In another aspect,suitable small molecule dyes include small molecule dyes selected fromthe group consisting of Colour Index (Society of Dyers and Colourists,Bradford, UK) numbers Acid Violet 17, Direct Blue 71, Direct Violet 51,Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 ormixtures thereof.

Suitable polymeric dyes include polymeric dyes selected from the groupconsisting of polymers containing conjugated chromogens (dye-polymerconjugates) and polymers with chromogens co-polymerized into thebackbone of the polymer and mixtures thereof.

In another aspect, suitable polymeric dyes include polymeric dyesselected from the group consisting of surface-substantive colorants soldunder the name of Liquitint® (Milliken, Spartanburg, S.C., USA),dye-polymer conjugates formed from at least one reactive dye and apolymer selected from the group consisting of polymers comprising amoiety selected from the group consisting of a hydroxyl moiety, aprimary amine moiety, a secondary amine moiety, a thiol moiety andmixtures thereof. In still another aspect, suitable polymeric dyesinclude polymeric dyes selected from the group consisting of Liquitint®(Milliken, Spartanburg, S.C., USA) Violet CT, carboxymethyl cellulose(CMC) conjugated with a reactive blue, reactive violet or reactive reddye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme,Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product codeS-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylatedthiophene polymeric colourants, and mixtures thereof.

Preferred hueing dyes include the whitening agents found in WO 08/87497A1. These whitening agents may be characterized by the followingstructure (I):

wherein R₁ and R₂ can independently be selected from:

a) [(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≤5; wherein y≥1; and wherein z=0 to 5;

b) R₁=alkyl, aryl or aryl alkyl and R₂=[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≤10; wherein y≥1; and wherein z=0 to 5;

c) R₁=[CH₂CH₂(OR₃)CH₂OR₄] and R₂=[CH₂CH₂(OR₃)CH₂OR₄]

wherein R₃ is selected from the group consisting of H, (CH₂CH₂O)_(z)H,and mixtures thereof; and wherein z=0 to 10;

wherein R₄ is selected from the group consisting of (C₁-C₁₆)alkyl, arylgroups, and mixtures thereof; and

d) wherein R1 and R2 can independently be selected from the aminoaddition product of styrene oxide, glycidyl methyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether,2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by theaddition of from 1 to 10 alkylene oxide units.

A preferred whitening agent of the present invention may becharacterized by the following structure (II):

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof wherein R″ is selected from thegroup consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; whereinx+y≤5; wherein y≥1; and wherein z=0 to 5.

A further preferred whitening agent of the present invention may becharacterized by the following structure (III):

This whitening agent is commonly referred to as “Violet DD”. Violet DDis typically a mixture having a total of 5 EO groups. This structure isarrived the following selection in Structure I of the following pendantgroups in “part a” above:

R1 R2 R′ R″ X Y R′ R″ x y a H H 3 1 H H 0 1 b H H 2 1 H H 1 1 c = b H H1 1 H H 2 1 d = a H H 0 1 H H 3 1

Further whitening agents of use include those described in USPN 200834511 A1 (Unilever). A preferred agent is “Violet 13”.

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay, and mixtures thereof. In another aspect, suitable dye clayconjugates include dye clay conjugates selected from the groupconsisting of one cationic/basic dye selected from the group consistingof C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I.Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through23, CI Basic Black 1 through 11, and a clay selected from the groupconsisting of Montmorillonite clay, Hectorite clay, Saponite clay andmixtures thereof. In still another aspect, suitable dye clay conjugatesinclude dye clay conjugates selected from the group consisting of:Montmorillonite Basic Blue B7 C.I. 42595 conjugate, MontmorilloniteBasic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I.42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate,Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I.Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate,Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite BasicBlue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite BasicRed R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate andmixtures thereof.

Suitable pigments include pigments selected from the group consisting offlavanthrone, indanthrone, chlorinated indanthrone containing from 1 to4 chlorine atoms, pyranthrone, dichloropyranthrone,monobromodichloropyranthrone, dibromodichloropyranthrone,tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide,wherein the imide groups may be unsubstituted or substituted byC1-C3-alkyl or a phenyl or heterocyclic radical, and wherein the phenyland heterocyclic radicals may additionally carry substituents which donot confer solubility in water, anthrapyrimidinecarboxylic acid amides,violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyaninewhich may contain up to 2 chlorine atoms per molecule, polychloro-copperphthalocyanine or polybromochloro-copper phthalocyanine containing up to14 bromine atoms per molecule and mixtures thereof.

In another aspect, suitable pigments include pigments selected from thegroup consisting of Ultramarine Blue (C.I. Pigment Blue 29), UltramarineViolet (C.I. Pigment Violet 15) and mixtures thereof.

The aforementioned fabric hueing agents can be used in combination (anymixture of fabric hueing agents can be used). Suitable fabric hueingagents can be purchased from Aldrich, Milwaukee, Wis., USA; CibaSpecialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany;Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., EastProvidence, R.I., USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen,Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland;Avecia, Manchester, UK and/or made in accordance with the examplescontained herein. Suitable hueing agents are described in more detail inU.S. Pat. No. 7,208,459 B2.

Enzymes

One or more enzymes may be present in the fibrous elements and/orparticles of the present invention. Non-limiting examples of suitableenzymes include proteases, amylases, lipases, cellulases, carbohydrasesincluding mannanases and endoglucanases, pectinases, hemicellulases,peroxidases, xylanases, phopholipases, esterases, cutinases,keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, penosanases, malanases, glucanases,arabinosidases, hyaluraonidases, chrondroitinases, laccases, andmixtures thereof.

Enzymes may be included in the fibrous elements and/or particles of thepresent invention for a variety of purposes, including but not limitedto removal of protein-based, carbohydrate-based, or triglyceride-basedstains from substrates, for the prevention of refugee dye transfer infabric laundering, and for fabric restoration. In one example, thefibrous elements and/or particles of the present invention may includeproteases, amylases, lipases, cellulases, peroxidases, and mixturesthereof of any suitable origin, such as vegetable, animal, bacterial,fungal and yeast origin. Selections of the enzymes utilized areinfluenced by factors such as pH-activity and/or stability optima,thermostability, and stability to other additives, such as activeagents, for example builders, present within the fibrous elements and/orparticles. In one example, the enzyme is selected from the groupconsisting of: bacterial enzymes (for example bacterial amylases and/orbacterial proteases), fungal enzymes (for example fungal cellulases),and mixtures thereof.

When present in the fibrous elements and/or particles of the presentinvention, the enzymes may be present at levels sufficient to provide a“cleaning-effective amount”. The term “cleaning effective amount” refersto any amount capable of producing a cleaning, stain removal, soilremoval, whitening, deodorizing, or freshness improving effect onsubstrates such as fabrics, dishware, flooring, porcelain and ceramics,metal surfaces and the like. In practical terms for current commercialpreparations, typical amounts are up to about 5 mg by weight, moretypically 0.01 mg to 3 mg, of active enzyme per gram of the fibrouselement and/or particle of the present invention. Stated otherwise, thefibrous elements and/or particles of the present invention willtypically comprise from about 0.001% to about 5% and/or from about 0.01%to about 3% and/or from about 0.01% to about 1% by weight on a dryfibrous element basis and/or dry particle basis and/or dry fibrousstructure basis.

One or more enzymes may be applied to the fibrous element and/orparticle after the fibrous element and/or particle is produced.

A range of enzyme materials and means for their incorporation into thefilament-forming composition of the present invention, which may be asynthetic detergent composition, is also disclosed in WO 9307263 A; WO9307260 A; WO 8908694 A; U.S. Pat. Nos. 3,553,139; 4,101,457; and U.S.Pat. No. 4,507,219.

Enzyme Stabilizing System

When enzymes are present in the fibrous elements and/or particles of thepresent invention, an enzyme stabilizing system may also be included inthe fibrous elements and/or particles. Enzymes may be stabilized byvarious techniques. Non-limiting examples of enzyme stabilizationtechniques are disclosed and exemplified in U.S. Pat. Nos. 3,600,319 and3,519,570; EP 199,405, EP 200,586; and WO 9401532 A.

In one example, the enzyme stabilizing system may comprise calciumand/or magnesium ions.

The enzyme stabilizing system may be present in the fibrous elementsand/or particles of the present invention at a level of from about0.001% to about 10% and/or from about 0.005% to about 8% and/or fromabout 0.01% to about 6% by weight on a dry fibrous element basis and/ordry particle basis and/or dry fibrous structure basis. The enzymestabilizing system can be any stabilizing system which is compatiblewith the enzymes present in the fibrous elements and/or particles. Suchan enzyme stabilizing system may be inherently provided by otherformulation actives, or be added separately, e.g., by the formulator orby a manufacturer of enzymes. Such enzyme stabilizing systems may, forexample, comprise calcium ion, magnesium ion, boric acid, propyleneglycol, short chain carboxylic acids, boronic acids, and mixturesthereof, and are designed to address different stabilization problems.

Heat Forming Agents

The fibrous elements and/or particles of the present invention maycontain a heat forming agent. Heat forming agents are formulated togenerate heat in the presence of water and/or oxygen (e.g., oxygen inthe air, etc.) and to thereby accelerate the rate at which the fibrousstructure degrades in the presence of water and/or oxygen, and/or toincrease the effectiveness of one or more of the actives in the fibrouselement. The heat forming agent can also or alternatively be used toaccelerate the rate of release of one or more actives from the fibrousstructure. The heat forming agent is formulated to undergo an exothermicreaction when exposed to oxygen (i.e., oxygen in the air, oxygen in thewater, etc.) and/or water. Many different materials and combination ofmaterials can be used as the heat forming agent. Non-limiting heatforming agents that can be used in the fibrous structure includeelectrolyte salts (e.g., aluminum chloride, calcium chloride, calciumsulfate, cupric chloride, cuprous chloride, ferric sulfate, magnesiumchloride, magnesium sulfate, manganese chloride, manganese sulfate,potassium chloride, potassium sulfate, sodium acetate, sodium chloride,sodium carbonate, sodium sulfate, etc.), glycols (e.g., propyleneglycol, dipropylenenglycol, etc.), lime (e.g., quick lime, slaked lime,etc.), metals (e.g., chromium, copper, iron, magnesium, manganese,etc.), metal oxides (e.g., aluminum oxide, iron oxide, etc.),polyalkyleneamine, polyalkyleneimine, polyvinyl amine, zeolites,gycerin, 1,3, propanediol, polysorbates esters (e.g., Tweens 20, 60, 85,80), and/or poly glycerol esters (e.g., Noobe, Drewpol and Drewmulzefrom Stepan). The heat forming agent can be formed of one or morematerials. For example, magnesium sulfate can singularly form the heatforming agent. In another non-limiting example, the combination of about2-25 weight percent activated carbon, about 30-70 weight percent ironpowder and about 1-10 weight percent metal salt can form the heatforming agent. As can be appreciated, other or additional materials canbe used alone or in combination with other materials to form the heatforming agent. Non-limiting examples of materials that can be used toform the heat forming agent used in a fibrous structure are disclosed inU.S. Pat. Nos. 5,674,270 and 6,020,040; and in U.S. Patent ApplicationPublication Nos. 2008/0132438 and 2011/0301070.

Degrading Accelerators

The fibrous elements and/or particles of the present invention maycontain a degrading accelerators used to accelerate the rate at which afibrous structure degrades in the presence of water and/or oxygen. Thedegrading accelerator, when used, is generally designed to release gaswhen exposed to water and/or oxygen, which in turn agitates the regionabout the fibrous structure so as to cause acceleration in thedegradation of a carrier film of the fibrous structure. The degradingaccelerator, when used, can also or alternatively be used to acceleratethe rate of release of one or more actives from the fibrous structure;however, this is not required. The degrading accelerator, when used, canalso or alternatively be used to increase the effectivity of one or moreof the actives in the fibrous structure; however, this is not required.The degrading accelerator can include one or more materials such as, butnot limited to, alkali metal carbonates (e.g. sodium carbonate,potassium carbonate, etc.), alkali metal hydrogen carbonates (e.g.,sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), ammoniumcarbonate, etc. The water soluble strip can optionally include one ormore activators that are used to activate or increase the rate ofactivation of the one or more degrading accelerators in the fibrousstructure. As can be appreciated, one or more activators can be includedin the fibrous structure even when no degrading accelerator exists inthe fibrous structure; however, this is not required. For instance, theactivator can include an acidic or basic compound, wherein such acidicor basic compound can be used as a supplement to one or more actives inthe fibrous structure when a degrading accelerator is or is not includedin the fibrous structure. Non-limiting examples of activators, whenused, that can be included in the fibrous structure include organicacids (e.g., hydroxy-carboxylic acids [citric acid, tartaric acid, malicacid, lactic acid, gluconic acid, etc.], saturated aliphatic carboxylicacids [acetic acid, succinic acid, etc.], unsaturated aliphaticcarboxylic acids [e.g., fumaric acid, etc.]. Non-limiting examples ofmaterials that can be used to form degrading accelerators and activatorsused in a fibrous structure are disclosed in U.S. Patent ApplicationPublication No. 2011/0301070.

Release of Active Agent

One or more active agents may be released from the fibrous elementand/or particle and/or fibrous structure when the fibrous element and/orparticle and/or fibrous structure is exposed to a triggering condition.In one example, one or more active agents may be released from thefibrous element and/or particle and/or fibrous structure or a partthereof when the fibrous element and/or particle and/or fibrousstructure or the part thereof loses its identity, in other words, losesits physical structure. For example, a fibrous element and/or particleand/or fibrous structure loses its physical structure when thefilament-forming material dissolves, melts or undergoes some othertransformative step such that its structure is lost. In one example, theone or more active agents are released from the fibrous element and/orparticle and/or fibrous structure when the fibrous element's and/orparticle's and/or fibrous structure's morphology changes.

In another example, one or more active agents may be released from thefibrous element and/or particle and/or fibrous structure or a partthereof when the fibrous element and/or particle and/or fibrousstructure or the part thereof alters its identity, in other words,alters its physical structure rather than loses its physical structure.For example, a fibrous element and/or particle and/or fibrous structurealters its physical structure when the filament-forming material swells,shrinks, lengthens, and/or shortens, but retains its filament-formingproperties.

In another example, one or more active agents may be released from thefibrous element and/or particle and/or fibrous structure with itsmorphology not changing (not losing or altering its physical structure).

In one example, the fibrous element and/or particle and/or fibrousstructure may release an active agent upon the fibrous element and/orparticle and/or fibrous structure being exposed to a triggeringcondition that results in the release of the active agent, such as bycausing the fibrous element and/or particle and/or fibrous structure tolose or alter its identity as discussed above. Non-limiting examples oftriggering conditions include exposing the fibrous element and/orparticle and/or fibrous structure to solvent, a polar solvent, such asalcohol and/or water, and/or a non-polar solvent, which may besequential, depending upon whether the filament-forming materialcomprises a polar solvent-soluble material and/or a non-polarsolvent-soluble material; exposing the fibrous element and/or particleand/or fibrous structure to heat, such as to a temperature of greaterthan 75° F. and/or greater than 100° F. and/or greater than 150° F.and/or greater than 200° F. and/or greater than 212° F.; exposing thefibrous element and/or particle and/or fibrous structure to cold, suchas to a temperature of less than 40° F. and/or less than 32° F. and/orless than 0° F.; exposing the fibrous element and/or particle and/orfibrous structure to a force, such as a stretching force applied by aconsumer using the fibrous element and/or particle and/or fibrousstructure; and/or exposing the fibrous element and/or particle and/orfibrous structure to a chemical reaction; exposing the fibrous elementand/or particle and/or fibrous structure to a condition that results ina phase change; exposing the fibrous element and/or particle and/orfibrous structure to a pH change and/or a pressure change and/ortemperature change; exposing the fibrous element and/or particle and/orfibrous structure to one or more chemicals that result in the fibrouselement and/or particle and/or fibrous structure releasing one or moreof its active agents; exposing the fibrous element and/or particleand/or fibrous structure to ultrasonics; exposing the fibrous elementand/or particle and/or fibrous structure to light and/or certainwavelengths; exposing the fibrous element and/or particle and/or fibrousstructure to a different ionic strength; and/or exposing the fibrouselement and/or particle and/or fibrous structure to an active agentreleased from another fibrous element and/or particle and/or fibrousstructure.

In one example, one or more active agents may be released from thefibrous elements and/or particles of the present invention when afibrous structure product comprising the fibrous elements and/orparticles is subjected to a triggering step selected from the groupconsisting of: pre-treating stains on a fabric article with the fibrousstructure product; forming a wash liquor by contacting the fibrousstructure product with water; tumbling the fibrous structure product ina dryer; heating the fibrous structure product in a dryer; andcombinations thereof.

Filament-Forming Composition

The fibrous elements of the present invention are made from afilament-forming composition. The filament-forming composition is apolar-solvent-based composition. In one example, the filament-formingcomposition is an aqueous composition comprising one or morefilament-forming materials and one or more active agents.

The filament-forming composition of the present invention may have ashear viscosity as measured according to the Shear Viscosity Test Methoddescribed herein of from about 1 Pascal·Seconds to about 25Pascal·Seconds and/or from about 2 Pascal·Seconds to about 20Pascal·Seconds and/or from about 3 Pascal·Seconds to about 10Pascal·Seconds, as measured at a shear rate of 3,000 sec⁻¹ and at theprocessing temperature (50° C. to 100° C.).

The filament-forming composition may be processed at a temperature offrom about 50° C. to about 100° C. and/or from about 65° C. to about 95°C. and/or from about 70° C. to about 90° C. when making fibrous elementsfrom the filament-forming composition.

In one example, the filament-forming composition may comprise at least20% and/or at least 30% and/or at least 40% and/or at least 45% and/orat least 50% to about 90% and/or to about 85% and/or to about 80% and/orto about 75% by weight of one or more filament-forming materials, one ormore active agents, and mixtures thereof. The filament-formingcomposition may comprise from about 10% to about 80% by weight of apolar solvent, such as water.

In one example, non-volatile components of the filament-formingcomposition may comprise from about 20% and/or 30% and/or 40% and/or 45%and/or 50% to about 75% and/or 80% and/or 85% and/or 90% by weight basedon the total weight of the filament-forming composition. Thenon-volatile components may be composed of filament-forming materials,such as backbone polymers, active agents and combinations thereof.Volatile components of the filament-forming composition will comprisethe remaining percentage and range from 10% to 80% by weight based onthe total weight of the filament-forming composition.

In a fibrous element spinning process, the fibrous elements need to haveinitial stability as they leave the spinning die. Capillary Number isused to characterize this initial stability criterion. At the conditionsof the die, the Capillary Number should be at least 1 and/or at least 3and/or at least 4 and/or at least 5.

In one example, the filament-forming composition exhibits a CapillaryNumber of from at least 1 to about 50 and/or at least 3 to about 50and/or at least 5 to about 30 such that the filament-forming compositioncan be effectively polymer processed into a fibrous element.

“Polymer processing” as used herein means any spinning operation and/orspinning process by which a fibrous element comprising a processedfilament-forming material is formed from a filament-forming composition.The spinning operation and/or process may include spun bonding, meltblowing, electro-spinning, rotary spinning, continuous filamentproducing and/or tow fiber producing operations/processes. A “processedfilament-forming material” as used herein means any filament-formingmaterial that has undergone a melt processing operation and a subsequentpolymer processing operation resulting in a fibrous element.

The Capillary number is a dimensionless number used to characterize thelikelihood of this droplet breakup. A larger capillary number indicatesgreater fluid stability upon exiting the die. The Capillary number isdefined as follows:

${Ca} = \frac{V \star \eta}{\sigma}$V is the fluid velocity at the die exit (units of Length per Time),η is the fluid viscosity at the conditions of the die (units of Mass perLength*Time),σ is the surface tension of the fluid (units of mass per Time²). Whenvelocity, viscosity, and surface tension are expressed in a set ofconsistent units, the resulting Capillary number will have no units ofits own; the individual units will cancel out.

The Capillary number is defined for the conditions at the exit of thedie. The fluid velocity is the average velocity of the fluid passingthrough the die opening. The average velocity is defined as follows:

$V = \frac{{Vol}^{\;\prime}}{Area}$Vol′=volumetric flowrate (units of Length³ per Time),Area=cross-sectional area of the die exit (units of Length²).

When the die opening is a circular hole, then the fluid velocity can bedefined as

$V = \frac{{Vol}^{\;\prime}}{\pi \star R^{2}}$R is the radius of the circular hole (units of length).

The fluid viscosity will depend on the temperature and may depend of theshear rate. The definition of a shear thinning fluid includes adependence on the shear rate. The surface tension will depend on themakeup of the fluid and the temperature of the fluid.

In one example, the filament-forming composition may comprise one ormore release agents and/or lubricants. Non-limiting examples of suitablerelease agents and/or lubricants include fatty acids, fatty acid salts,fatty alcohols, fatty esters, sulfonated fatty acid esters, fatty amineacetates and fatty amides, silicones, aminosilicones, fluoropolymers andmixtures thereof.

In one example, the filament-forming composition may comprise one ormore antiblocking and/or detackifying agents. Non-limiting examples ofsuitable antiblocking and/or detackifying agents include starches,modified starches, crosslinked polyvinylpyrrolidone, crosslinkedcellulose, microcrystalline cellulose, silica, metallic oxides, calciumcarbonate, talc and mica.

Active agents of the present invention may be added to thefilament-forming composition prior to and/or during fibrous elementformation and/or may be added to the fibrous element after fibrouselement formation. For example, a perfume active agent may be applied tothe fibrous element and/or fibrous structure comprising the fibrouselement after the fibrous element and/or fibrous structure according tothe present invention are formed. In another example, an enzyme activeagent may be applied to the fibrous element and/or fibrous structurecomprising the fibrous element after the fibrous element and/or fibrousstructure according to the present invention are formed. In stillanother example, one or more particles, which may not be suitable forpassing through the spinning process for making the fibrous element, maybe applied to the fibrous element and/or fibrous structure comprisingthe fibrous element after the fibrous element and/or fibrous structureaccording to the present invention are formed.

Extensional Aids

In one example, the fibrous element comprises an extensional aid.Non-limiting examples of extensional aids can include polymers, otherextensional aids, and combinations thereof.

In one example, the extensional aids have a weight-average molecularweight of at least about 500,000 Da. In another example, the weightaverage molecular weight of the extensional aid is from about 500,000 toabout 25,000,000, in another example from about 800,000 to about22,000,000, in yet another example from about 1,000,000 to about20,000,000, and in another example from about 2,000,000 to about15,000,000. The high molecular weight extensional aids are preferred insome examples of the invention due to the ability to increaseextensional melt viscosity and reducing melt fracture.

The extensional aid, when used in a meltblowing process, is added to thecomposition of the present invention in an amount effective to visiblyreduce the melt fracture and capillary breakage of fibers during thespinning process such that substantially continuous fibers havingrelatively consistent diameter can be melt spun. Regardless of theprocess employed to produce fibrous elements and/or particles, theextensional aids, when used, can be present from about 0.001% to about10%, by weight on a dry fibrous element basis and/or dry particle basisand/or dry fibrous structure basis, in one example, and in anotherexample from about 0.005 to about 5%, by weight on a dry fibrous elementbasis and/or dry particle basis and/or dry fibrous structure basis, inyet another example from about 0.01 to about 1%, by weight on a dryfibrous element basis and/or dry particle basis and/or dry fibrousstructure basis, and in another example from about 0.05% to about 0.5%,by weight on a dry fibrous element basis and/or dry particle basisand/or dry fibrous structure basis.

Non-limiting examples of polymers that can be used as extensional aidscan include alginates, carrageenans, pectin, chitin, guar gum, xanthumgum, agar, gum arabic, karaya gum, tragacanth gum, locust bean gum,alkylcellulose, hydroxyalkylcellulose, carboxyalkylcellulose, andmixtures thereof.

Nonlimiting examples of other extensional aids can include modified andunmodified polyacrylamide, polyacrylic acid, polymethacrylic acid,polyvinyl alcohol, polyvinylacetate, polyvinylpyrrolidone, polyethylenevinyl acetate, polyethyleneimine, polyamides, polyalkylene oxidesincluding polyethylene oxide, polypropylene oxide, polyethylenepropyleneoxide, and mixtures thereof.

Method for Making Fibrous Elements

The fibrous elements of the present invention may be made by anysuitable process. A non-limiting example of a suitable process formaking the fibrous elements is described below.

In one example, as shown in FIGS. 9 and 10. a method 46 for making afibrous element 32 according to the present invention comprises thesteps of:

a. providing a filament-forming composition 48 comprising one or morefilament-forming materials, and optionally one or more active agents;and

b. spinning the filament-forming composition 48, such as via a spinningdie 50, into one or more fibrous elements 32, such as filaments,comprising the one or more filament-forming materials and optionally,the one or more active agents. The one or more active agents may bereleasable from the fibrous element when exposed to conditions ofintended use. The total level of the one or more filament-formingmaterials present in the fibrous element 32, when active agents arepresent therein, may be less than 80% and/or less than 70% and/or lessthan 65% and/or 50% or less by weight on a dry fibrous element basisand/or dry fibrous structure basis and the total level of the one ormore active agents, when present in the fibrous element may be greaterthan 20% and/or greater than 35% and/or 50% or greater 65% or greaterand/or 80% or greater by weight on a dry fibrous element basis and/ordry fibrous structure basis.

As shown in FIG. 10, the spinning die 50 may comprise a plurality offibrous element-forming holes 52 that include a melt capillary 54encircled by a concentric attenuation fluid hole 56 through which afluid, such as air, passes to facilitate attenuation of thefilament-forming composition 48 into a fibrous element 32 as it exitsthe fibrous element-forming hole 52.

In one example, during the spinning step, any volatile solvent, such aswater, present in the filament-forming composition 48 is removed, suchas by drying, as the fibrous element 32 is formed. In one example,greater than 30% and/or greater than 40% and/or greater than 50% of theweight of the filament-forming composition's volatile solvent, such aswater, is removed during the spinning step, such as by drying thefibrous element being produced.

The filament-forming composition may comprise any suitable total levelof filament-forming materials and any suitable level of active agents solong as the fibrous element produced from the filament-formingcomposition comprises a total level of filament-forming materials in thefibrous element of from about 5% to 50% or less by weight on a dryfibrous element basis and/or dry particle basis and/or dry fibrousstructure basis and a total level of active agents in the fibrouselement of from 50% to about 95% by weight on a dry fibrous elementbasis and/or dry particle basis and/or dry fibrous structure basis.

In one example, the filament-forming composition may comprise anysuitable total level of filament-forming materials and any suitablelevel of active agents so long as the fibrous element produced from thefilament-forming composition comprises a total level of filament-formingmaterials in the fibrous element and/or particle of from about 5% to 50%or less by weight on a dry fibrous element basis and/or dry particlebasis and/or dry fibrous structure basis and a total level of activeagents in the fibrous element and/or particle of from 50% to about 95%by weight on a dry fibrous element basis and/or dry particle basisand/or dry fibrous structure basis, wherein the weight ratio offilament-forming material to total level of active agents is 1 or less.

In one example, the filament-forming composition comprises from about 1%and/or from about 5% and/or from about 10% to about 50% and/or to about40% and/or to about 30% and/or to about 20% by weight of thefilament-forming composition of filament-forming materials; from about1% and/or from about 5% and/or from about 10% to about 50% and/or toabout 40% and/or to about 30% and/or to about 20% by weight of thefilament-forming composition of active agents; and from about 20% and/orfrom about 25% and/or from about 30% and/or from about 40% and/or toabout 80% and/or to about 70% and/or to about 60% and/or to about 50% byweight of the filament-forming composition of a volatile solvent, suchas water. The filament-forming composition may comprise minor amounts ofother active agents, such as less than 10% and/or less than 5% and/orless than 3% and/or less than 1% by weight of the filament-formingcomposition of plasticizers, pH adjusting agents, and other activeagents.

The filament-forming composition is spun into one or more fibrouselements and/or particles by any suitable spinning process, such asmeltblowing, spunbonding, electro-spinning, and/or rotary spinning. Inone example, the filament-forming composition is spun into a pluralityof fibrous elements and/or particles by meltblowing. For example, thefilament-forming composition may be pumped from a tank to a meltblownspinnerette. Upon exiting one or more of the filament-forming holes inthe spinnerette, the filament-forming composition is attenuated with airto create one or more fibrous elements and/or particles. The fibrouselements and/or particles may then be dried to remove any remainingsolvent used for spinning, such as the water.

The fibrous elements and/or particles of the present invention may becollected on a belt, such as a patterned belt to form a fibrousstructure comprising the fibrous elements and/or particles.

Method for Making Fibrous Structures

As shown in FIG. 11, a fibrous structure 28 of the present invention maybe made by spinning a filament-forming composition from a spinning die50, as described in FIGS. 9 and 10, to form a plurality of fibrouselements 32, such as filaments, and then associating one or moreparticles 36 provided by a particle source 58, for example a sifter or aairlaid forming head. The particles 36 may be dispersed within thefibrous elements 32. The mixture of particles 36 and fibrous elements 32may be collected on a collection belt 60, such as a patterned collectionbelt that imparts a texture, such as a three-dimensional texture to atleast one surface of the fibrous structure 28.

FIG. 12 illustrates an example of a method for making a fibrousstructure 28 according to FIG. 6. The method comprises the steps offorming a first layer 30 of a plurality of fibrous elements 32 such thatpockets 38 are formed in a surface of the first layer 30. One or moreparticles 36 are deposited into the pockets 38 from a particle source58. A second layer 34 comprising a plurality of fibrous elements 32produced from a spinning die 50 are then formed on the surface of thefirst layer 30 such that the particles 36 are entrapped in the pockets38.

FIG. 13 illustrates yet another example of a method for making a fibrousstructure 28 according to FIG. 5. The method comprises the steps offorming a first layer 30 of a plurality of fibrous elements 32. One ormore particles 36 are deposited onto a surface of the first layer 30from a particle source 58. A second layer 34 comprising a plurality offibrous elements 32 produced from a spinning die 50 are then formed ontop of the particles 36 such that the particles 36 are positionedbetween the first layer 30 and the second layer 34.

Non-Limiting Examples for Making Fibrous Structures

The addition of particles may be accomplished during the formation ofthe embryonic fibers or after collection of the embryonic fibers on thepatterned belts. Disclosed are three methods involving the addition ofparticulates resulting in said particulates being entrapped in thestructure

As shown in FIGS. 9 and 10, the fibrous elements of the presentinvention may be made as follows. Fibrous elements may be formed bymeans of a small-scale apparatus, a schematic representation of which isshown in FIGS. 9 and 10. A pressurized tank 62, suitable for batchoperation is filled with a suitable filament-forming composition 48 forspinning. A pump 64, such as a Zenith®, type PEP II, having a capacityof 5.0 cubic centimeters per revolution (cc/rev), manufactured by ParkerHannifin Corporation, Zenith Pumps division, of Sanford, N.C., USA maybe used to facilitate transport of the filament-forming composition to aspinning die 50. The flow of the filament-forming composition 48 fromthe pressurized tank 62 to the spinning die 50 may be controlled byadjusting the number of revolutions per minute (rpm) of the pump 64.Pipes 66 are used to connect the pressurized tank 62, the pump 64, andthe spinning die 50.

The spinning die 50 shown in FIG. 10 has several rows of circularextrusion nozzles (fibrous element-forming holes 52) spaced from oneanother at a pitch P of about 1.524 millimeters (about 0.060 inches).The nozzles have individual inner diameters of about 0.305 millimeters(about 0.012 inches) and individual outside diameters of about 0.813millimeters (about 0.032 inches). Each individual nozzle is encircled byan annular and divergently flared orifice (concentric attenuation fluidhole 56 to supply attenuation air to each individual melt capillary 54.The filament-forming composition 48 extruded through the nozzles issurrounded and attenuated by generally cylindrical, humidified airstreams supplied through the orifices.

Attenuation air can be provided by heating compressed air from a sourceby an electrical-resistance heater, for example, a heater manufacturedby Chromalox, Division of Emerson Electric, of Pittsburgh, Pa., USA. Anappropriate quantity of steam was added to saturate or nearly saturatethe heated air at the conditions in the electrically heated,thermostatically controlled delivery pipe. Condensate was removed in anelectrically heated, thermostatically controlled, separator.

The embryonic fibrous element are dried by a drying air stream having atemperature from about 149° C. (about 300° F.) to about 315° C. (about600° F.) by an electrical resistance heater (not shown) supplied throughdrying nozzles and discharged at an angle of about 90 degrees relativeto the general orientation of the non-thermoplastic embryonic fibersbeing extruded. The dried embryonic fibrous elements are collected on acollection device, such as, for example, a movable foraminous belt orpatterned collection belt. The addition of a vacuum source directlyunder the formation zone may be used to aid collection of the fibers.

Example 1

A first layer of fibrous elements is spun and collected on a patternedcollection belt. The belt chosen for this example is shown in FIG. 14.The resulting first layer comprises pockets that extend in thez-direction of the first layer and ultimately the fibrous structureformed therefrom. The pockets are suitable for receiving particles. Thefirst layer is left on the collection belt.

Table 1 below sets forth is an example of a filament-forming compositionof the present invention, which is used to make the fibrous elements inthese non-limiting examples. This filament-forming composition is madeand placed in the pressurized tank 62 in FIG. 9.

TABLE 1 % by weight of Filament filament- (i.e., forming Filament-components composition Forming remaining % by weight (i.e., Compositionupon drying) on a dry premix) (%) (%) filament basis C12-15 AES 28.4511.38 11.38 28.07 C11.8 HLAS 12.22 4.89 4.89 12.05 MEA 7.11 2.85 2.857.02 N67HSAS 4.51 1.81 1.81 4.45 Glycerol 3.08 1.23 1.23 3.04 PE-20,3.00 1.20 1.20 2.95 Polyethyleneimine Ethoxylate, PEI 600 E20Ethoxylated/Propoxylated 2.95 1.18 1.18 2.91 PolyethyleneimineBrightener 15 2.20 0.88 0.88 2.17 Amine Oxide 1.46 0.59 0.59 1.44 Sasol24,9 Nonionic 1.24 0.50 0.50 1.22 Surfactant DTPA (Chelant) 1.08 0.430.43 1.06 Tiron (Chelant) 1.08 0.43 0.43 1.06 Celvol 523 PVOH¹ 0.00013.20 13.20 32.55 Water 31.63 59.43 ¹Celvol 523, Celanese/Sekisui, MW85,000-124,000, 87-89% hydrolyzed

Particles are then spread out over the first layer to fill the pockets.In this case, Green Zero (Green Speckle Granules) manufactured byGenencor International® of Leiden, The Netherlands are used. The pocketsranged from being completely full of to completely empty of particles.This step is shown in FIG. 5.

The collection belt, still carrying the first layer with particlesthereon, is passed under a spinning die, which provides a second layerof a plurality of fibrous elements. The collection belt is usedthroughout the entire process to help maintain the integrity of thepocket pattern within the resulting fibrous structure. As the collectionbelt passes under the spinning die that provides the second layer, a“cap layer” is formed which entraps the particles in the pockets betweenthe first layer and second layer. An example of the resulting product isshown in FIG. 6. While a dual pass process using a single spinning dieis used to construct this fibrous structure, a single pass process usingmultiple spinning dies can be used.

The resulting fibrous structure exhibited the following data as shown inTables 2-5 below.

TABLE 2 MD MD Basis Thick- Tensile Peak MD MD Inventive Weight nessStrength Elongation TEA Modulus Example g/m² Microns g/in % g*in/in²g/cm 1 105.7 866.8 506.9 70.7 263 1266

TABLE 3 CD CD Basis Thick- Tensile Peak CD Inventive Weight nessStrength Elongation CDTEA Modulus Example g/m² Microns g/in % g*in/in²g/cm 1 105.7 866.8 464.9 102.1 164 773

TABLE 4 Geometric Geometric Basis Mean Tensile Mean Peak GeometricGeometric Inventive Weight Thickness Strength Elongation Mean TEA MeanModulus Example g/m² Microns g/in % g*in/in² g/cm 1 105.7 866.8 485.485.0 208 989

TABLE 5 Basis Weight normalized Inventive Basis weight Dissolutiondissolution Example (gsm) time (s) time (s/gsm) 1 105.8 67.5 0.64

Example 2

A particle source, for example a feeder, suitable to supply a flow ofparticles is placed directly above the drying region for the fibrouselements as shown in FIG. 11. In this case a vibratory feeder made byRetsch® of Haan, Germany, is used. In order to aid in a consistentdistribution of particles in the cross direction the particles are fedonto a tray that started off the width of the feeder and ended at thesame width as the spinning die face to ensure particles were deliveredinto all areas of fibrous element formation. The tray is completelyenclosed with the exception of the exit to minimize disruption of theparticle feed.

While embryonic fibrous elements are being formed, the feeder is turnedon and particles are introduced into the fibrous element stream. In thiscase, Green Zero (Green Speckle Granules) manufactured by GenencorInternational® of Leiden, The Netherlands is used as the particles. Theparticles associated and/or mixed with the fibrous elements and arecollected together on the collecting belt.

Example 3

The fibrous structure from Example 2 is used as a first layer for thefibrous structure of this Example. The first layer is passed under aspinning die twice such that both the top and bottom of the first layerwas exposed to the fibrous elements being produced by the spinning die,thereby creating a tri-layered fibrous structure.

Automatic Dishwashing Articles

Automatic dishwashing articles comprise one or more fibrous structuresof the present invention and a surfactant system, and optionally one ormore optional ingredients known in the art of cleaning, for exampleuseful in cleaning dishware in an automatic dishwashing machine.Examples of these optional ingredients include: anti-scalants, chelants,bleaching agents, perfumes, dyes, antibacterial agents, enzymes (e.g.,protease, amylase), cleaning polymers (e.g., alkoxylatedpolyethyleneimine polymer), anti-redeposition polymers, hydrotropes,suds inhibitors, carboxylic acids, thickening agents, preservatives,disinfecting agents, glass and metal care agents, pH buffering means sothat the automatic dishwashing liquor generally has a pH of from 3 to 14(alternatively 8 to 11), or mixtures thereof. Examples of automaticdishwashing actives are described in U.S. Pat. Nos. 5,679,630;5,703,034; 5,703,034; 5,705,464; 5,962,386; 5,968,881; 6,017,871;6,020,294.

Scale formation can be a problem. It can result from precipitation ofalkali earth metal carbonates, phosphates, and silicates. Examples ofanti-scalants include polyacrylates and polymers based on acrylic acidcombined with other moieties. Sulfonated varieties of these polymers areparticular effective in nil phosphate formulation executions. Examplesof anti-scalants include those described in U.S. Pat. No. 5,783,540,col. 15, 1. 20-col. 16, 1. 2; and EP 0 851 022 A2, pg. 12, 1. 1-20.

In one example, an automatic dishwashing article comprising a fibrousstructure of the present invention may contain a dispersant polymertypically in the range from 0 to about 30% and/or from about 0.5% toabout 20% and/or from about 1% to about 10% by weight of the automaticdishwashing article. The dispersant polymer may be ethoxylated cationicdiamines or ethoxylated cationic polyamines described in U.S. Pat. No.4,659,802. Other suitable dispersant polymers include co-polymerssynthesized from acrylic acid, maleic acid and methacrylic acid such asACUSOL® 480N and ACUSOL 588® supplied by Rohm & Haas and anacrylic-maleic (ratio 80/20) phosphono end group dispersant copolymerssold under the tradename of Acusol 425N® available from Rohm &Haas.Polymers containing both carboxylate and sulphonate monomers, such asALCOSPERSE® polymers (supplied by Alco) are also acceptable dispersantpolymers. In one embodiment an ALCOSPERSE® polymer sold under the tradename ALCOSPERSE® 725, is a copolymer of Styrene and Acrylic Acid.ALCOSPERSE® 725 may also provide a metal corrosion inhibition benefit.Other dispersant polymers are low molecular weight modified polyacrylatecopolymers including the low molecular weight copolymers of unsaturatedaliphatic carboxylic acids disclosed in U.S. Pat. Nos. 4,530,766, and5,084,535 and European Patent Application No. 66,915, published Dec. 15,1982.

In one embodiment, an automatic dishwashing article comprising a fibrousstructure of the present invention may contain a nonionic surfactant, asulfonated polymer, optionally a chelant, optionally a builder, andoptionally a bleaching agent, and mixtures thereof. A method of cleaningdishware is provided comprising the step of dosing an automaticdishwashing article of the present invention into an automaticdishwashing machine.

Hand Dishwashing Articles

Hand dish washing articles comprise one or more fibrous structures ofthe present invention that contains a surfactant system, and optionallyone or more optional ingredients known in the art of cleaning and handcare, for example useful in cleaning dishware by hand. Examples of theseoptional ingredients include: perfume, dyes, pearlescent agents,antibacterial agents, enzymes (e.g., protease), cleaning polymers (e.g.,alkoxylated polyethyleneimine polymer), cationic polymers, hydrotropes,humectants, emollients, hand care agents, polymeric suds stabilizers,bleaching agent, diamines, carboxylic acids, thickening agents,preservatives, disinfecting agents, pH buffering means so that the dishwashing liquor generally has a pH of from 3 to 14 and/or from 8 to 11,or mixtures thereof. Examples of hand dishwashing actives are describedin U.S. Pat. Nos. 5,990,065; and 6,060,122.

In one embodiment, the surfactant of the hand dishwashing articlecomprises an alkyl sulfate, an alkoxy sulfate, an alkyl sulfonate, analkoxy sulfonate, an alkyl aryl sulfonate, an amine oxide, a betaine ora derivative of aliphatic or heterocyclic secondary and ternary amine, aquaternary ammonium surfactant, an amine, a singly or multiplyalkoxylated alcohol, an alkyl polyglycoside, a fatty acid amidesurfactant, a C₈-C₂₀ ammonia amide, a monoethanolamide, adiethanolamide, an isopropanolamide, a polyhydroxy fatty acid amide, ora mixture thereof.

A method of washing dishware is provided comprising the step of dosing ahand dishwashing article of the present invention in a sink or basinsuitable for containing soiled dishware. The sink or basin may containwater and/or soiled dishware.

Hard Surface Cleaning Article

Hard surface cleaning articles comprise one or more fibrous structuresof the present invention that contains one or more ingredients known inthe art of cleaning, for example useful in cleaning hard surfaces, suchas an acid constituent, for example an acid constituent that providesgood limescale removal performance (e.g., formic acid, citric acid,sorbic acid, acetic acid, boric acid, maleic acid, adipic acid, lacticacid malic acid, malonic acid, glycolic acid, or mixtures thereof).Examples of ingredients that may be included an acidic hard surfacecleaning article may include those described in U.S. Pat. No. 7,696,143.Alternatively the hard surface cleaning article comprises an alkalinityconstituent (e.g., alkanolamine, carbonate, bicarbonate compound, ormixtures thereof). Examples of ingredients that may be included in analkaline hard surface cleaning article may include those described in US2010/0206328 A1. A method of cleaning a hard surface includes using ordosing a hard surface cleaning article in a method to clean a hardsurface. In one embodiment, the method comprises dosing a hard surfacecleaning article in a bucket or similar container, optionally addingwater to the bucket before or after dosing the article to the bucket. Inanother embodiment, the method comprising dosing a hard surface cleaningarticle in a toilet bowl, optionally scrubbing the surface of the toiletbowl after the article has dissolved in the water contained in thetoilet bowl.

Toilet Bowl Cleaning Head

A toilet bowl cleaning head for a toilet bowl cleaning implementcomprising one or more fibrous structures of the present invention isprovided. The toilet bowl cleaning head may be disposable. The toiletbowl cleaning head may be removably attached to a handle, so that theuser's hands remain remote from the toilet bowl. In one embodiment, thetoilet bowl cleaning head may contain a water dispersible shell. Inturn, the water dispersible shell may comprise one or more fibrousstructures of the present invention. This water dispersible shell mayencase a core. The core may comprise at least one granular material. Thegranular material of the core may comprise surfactants, organic acids,perfumes, disinfectants, bleaches, detergents, enzymes, particulates, ormixtures thereof. Optionally, the core may be free from cellulose, andmay comprise one or more fibrous structures of the present invention.Examples a suitable toilet bowl cleaning head may be made according tocommonly assigned U.S. Pat. No. 8,641,311. A suitable toilet bowlcleaning head containing starch materials may be made according tocommonly assigned U.S. Pat. Nos. 8,763,192; 8,726,444 and/or US patentapplication publication number 2012/0246854 A1. A method of cleaning atoilet bowl surface is provided comprising the step of contacting thetoilet bowl surface with a toilet bowl cleaning head of the presentinvention.

Methods of Use

The fibrous structures of the present invention comprising one or morefabric care active agents according the present invention may beutilized in a method for treating a fabric article. The method oftreating a fabric article may comprise one or more steps selected fromthe group consisting of: (a) pre-treating the fabric article beforewashing the fabric article; (b) contacting the fabric article with awash liquor formed by contacting the fibrous structure with water; (c)contacting the fabric article with the fibrous structure in a dryer; (d)drying the fabric article in the presence of the fibrous structure in adryer; and (e) combinations thereof.

In some embodiments, the method may further comprise the step ofpre-moistening the fibrous structure prior to contacting it to thefabric article to be pre-treated. For example, the fibrous structure canbe pre-moistened with water and then adhered to a portion of the fabriccomprising a stain that is to be pre-treated. Alternatively, the fabricmay be moistened and the fibrous structure placed on or adhered thereto.In some embodiments, the method may further comprise the step ofselecting of only a portion of the fibrous structure for use in treatinga fabric article. For example, if only one fabric care article is to betreated, a portion of the fibrous structure may be cut and/or torn awayand either placed on or adhered to the fabric or placed into water toform a relatively small amount of wash liquor which is then used topre-treat the fabric. In this way, the user may customize the fabrictreatment method according to the task at hand. In some embodiments, atleast a portion of a fibrous structure may be applied to the fabric tobe treated using a device. Exemplary devices include, but are notlimited to, brushes, sponges and tapes. In yet another embodiment, thefibrous structure may be applied directly to the surface of the fabric.Any one or more of the aforementioned steps may be repeated to achievethe desired fabric treatment benefit.

Test Methods

Unless otherwise specified, all tests described herein including thosedescribed under the Definitions section and the following test methodsare conducted on samples that have been conditioned in a conditionedroom at a temperature of 23° C.±1.0° C. and a relative humidity of50%±2% for a minimum of 2 hours prior to the test. The samples testedare “usable units.” “Usable units” as used herein means sheets, flatsfrom roll stock, pre-converted flats, and/or single or multi-plyproducts. All tests are conducted under the same environmentalconditions and in such conditioned room. Do not test samples that havedefects such as wrinkles, tears, holes, and like. Samples conditioned asdescribed herein are considered dry samples (such as “dry filaments”)for testing purposes. All instruments are calibrated according tomanufacturer's specifications.

Basis Weight Test Method

Basis weight of a fibrous structure is measured on stacks of twelveusable units using a top loading analytical balance with a resolution of±0.001 g. The balance is protected from air drafts and otherdisturbances using a draft shield. A precision cutting die, measuring3.500 in ±0.0035 in by 3.500 in ±0.0035 in is used to prepare allsamples.

With a precision cutting die, cut the samples into squares. Combine thecut squares to form a stack twelve samples thick. Measure the mass ofthe sample stack and record the result to the nearest 0.001 g.

The Basis Weight is calculated in lbs/3000 ft² or g/m² as follows:Basis Weight=(Mass of stack)/[(Area of 1 square in stack)×(No. ofsquares in stack)]For example,Basis Weight (lbs/3000 ft²)=[[Mass of stack (g)/453.6 (g/lbs)]/[12.25(in²)/144 (in²/ft²)×12]]×3000or,Basis Weight (g/m²)=Mass of stack (g)/[79.032 (cm²)/10,000 (cm²/m²)×12]Report result to the nearest 0.1 lbs/3000 ft² or 0.1 g/m². Sampledimensions can be changed or varied using a similar precision cutter asmentioned above, so as at least 100 square inches of sample area instack.Water Content Test Method

The water (moisture) content present in a fibrous element and/orparticle and/or fibrous structure is measured using the following WaterContent Test Method. A fibrous element and/or particle and/or fibrousstructure or portion thereof (“sample”) in the form of a pre-cut sheetis placed in a conditioned room at a temperature of 23° C.±1.0° C. and arelative humidity of 50%±2% for at least 24 hours prior to testing. Eachfibrous structure sample has an area of at least 4 square inches, butsmall enough in size to fit appropriately on the balance weighing plate.Under the temperature and humidity conditions mentioned above, using abalance with at least four decimal places, the weight of the sample isrecorded every five minutes until a change of less than 0.5% of previousweight is detected during a 10 minute period. The final weight isrecorded as the “equilibrium weight”. Within 10 minutes, the samples areplaced into the forced air oven on top of foil for 24 hours at 70° C.±2°C. at a relative humidity of 4%±□2% for drying. After the 24 hours ofdrying, the sample is removed and weighed within 15 seconds. This weightis designated as the “dry weight” of the sample.

The water (moisture) content of the sample is calculated as follows:

${\%\mspace{14mu}{Water}\mspace{14mu}{in}\mspace{14mu}{sample}} = {100\% \times \frac{\begin{matrix}\left( {{{Equilibrium}\mspace{14mu}{weight}\mspace{14mu}{of}\mspace{14mu}{sample}} -} \right. \\\left. {{Dry}\mspace{14mu}{weight}\mspace{14mu}{of}\mspace{14mu}{sample}} \right)\end{matrix}}{{Dry}\mspace{14mu}{weight}\mspace{14mu}{of}\mspace{14mu}{sample}}}$The % Water (moisture) in sample for 3 replicates is averaged to givethe reported % Water (moisture) in sample. Report results to the nearest0.1%.Dissolution Test Method

Apparatus and Materials (Also, See FIGS. 15 Though 17):

600 mL Beaker 12

Magnetic Stirrer 14 (Labline Model No. 1250 or equivalent)

Magnetic Stirring Rod 16 (5 cm)

Thermometer (1 to 100° C.+/−1° C.)

Cutting Die—Stainless Steel cutting die with dimensions 3.8 cm×3.2 cm

Timer (0-3,600 seconds or 1 hour), accurate to the nearest second. Timerused should have sufficient total time measurement range if sampleexhibits dissolution time greater than 3,600 seconds. However, timerneeds to be accurate to the nearest second.

Polaroid 35 mm Slide Mount 20 (commercially available from PolaroidCorporation or equivalent)-)

35 mm Slide Mount Holder 25 (or equivalent)

City of Cincinnati Water or equivalent having the following properties:Total Hardness=155 mg/L as CaCO₃; Calcium content=33.2 mg/L; Magnesiumcontent=17.5 mg/L; Phosphate content=0.0462.

Test Protocol

Equilibrate samples in constant temperature and humidity environment of23° C.±1.0° C. and 50% RH±2% for at least 2 hours. Measure the basisweight of the fibrous structure sample to be measured using Basis WeightTest Method defined herein. Cut three dissolution test specimens fromthe fibrous structure sample using cutting die (3.8 cm×3.2 cm), so itfits within the 35 mm Slide Mount 20, which has an open area dimensions24×36 mm. Lock each specimen in a separate 35 mm slide mount 20. Placemagnetic stirring rod 16 into the 600 mL beaker 12. Turn on the citywater tap flow (or equivalent) and measure water temperature withthermometer and, if necessary, adjust the hot or cold water to maintainit at the testing temperature. Testing temperature is 15° C.±1° C.water. Once at testing temperature, fill beaker 12 with 500 mL±5 mL ofthe 15° C.±1° C. city water. Place full beaker 12 on magnetic stirrer14, turn on stirrer 14, and adjust stir speed until a vortex developsand the bottom of the vortex is at the 400 mL mark on the beaker 12.Secure the 35 mm slide mount 20 in the alligator clamp 26 of the 35 mmslide mount holder 25 such that the long end 21 of the slide mount 20 isparallel to the water surface. The alligator clamp 26 should bepositioned in the middle of the long end 21 of the slide mount 20. Thedepth adjuster 28 of the holder 25 should be set so that the distancebetween the bottom of the depth adjuster 28 and the bottom of thealligator clip 26 is −11+/−0.125 inches. This set up will position thesample surface perpendicular to the flow of the water. In one motion,drop the secured slide and clamp into the water and start the timer. Thesample is dropped so that the sample is centered in the beaker.Disintegration occurs when the nonwoven structure breaks apart. Recordthis as the disintegration time. When all of the visible nonwovenstructure is released from the slide mount, raise the slide out of thewater while continuing the monitor the solution for undissolved nonwovenstructure fragments. Dissolution occurs when all nonwoven structurefragments are no longer visible. Record this as the dissolution time.

Three replicates of each sample are run and the average disintegrationand dissolution times are recorded. Average disintegration anddissolution times are in units of seconds.

The average disintegration and dissolution times are normalized forbasis weight by dividing each by the sample basis weight as determinedby the Basis Weight Method defined herein. Basis weight normalizeddisintegration and dissolution times are in units of seconds/gsm ofsample (s/(g/m²)).

Median Particle Size Test Method

This test method must be used to determine median particle size.

The median particle size test is conducted to determine the medianparticle size of the seed material using ASTM D 502-89, “Standard TestMethod for Particle Size of Soaps and Other Detergents”, approved May26, 1989, with a further specification for sieve sizes used in theanalysis. Following section 7, “Procedure using machine-sieving method,”a nest of clean dry sieves containing U.S. Standard (ASTM E 11) sieves#8 (2360 um), #12 (1700 um), #16 (1180 um), #20 (850 um), #30 (600 um),#40 (425 um), #50 (300 um), #70 (212 um), #100 (150 um) is required. Theprescribed Machine-Sieving Method is used with the above sieve nest. Theseed material is used as the sample. A suitable sieve-shaking machinecan be obtained from W.S. Tyler Company of Mentor, Ohio, U.S.A.

The data are plotted on a semi-log plot with the micron size opening ofeach sieve plotted against the logarithmic abscissa and the cumulativemass percent (Q₃) plotted against the linear ordinate. An example of theabove data representation is given in ISO 9276-1:1998, “Representationof results of particle size analysis—Part 1: Graphical Representation”,Figure A.4. The seed material median particle size (D₅₀), for thepurpose of this invention, is defined as the abscissa value at the pointwhere the cumulative mass percent is equal to 50 percent, and iscalculated by a straight line interpolation between the data pointsdirectly above (a50) and below (b50) the 50% value using the followingequation:D ₅₀=10^[Log(D _(a50))−(Log(D _(a50))−Log(D _(b50)))*(Q _(a50)−50%)/(Q_(a50) −Q _(b50))]where Q_(a50) and Q_(b50) are the cumulative mass percentile values ofthe data immediately above and below the 50^(th) percentile,respectively; and D_(a50) and D_(b50) are the micron sieve size valuescorresponding to these data.

In the event that the 50^(th) percentile value falls below the finestsieve size (150 um) or above the coarsest sieve size (2360 um), thenadditional sieves must be added to the nest following a geometricprogression of not greater than 1.5, until the median falls between twomeasured sieve sizes.

The Distribution Span of the Seed Material is a measure of the breadthof the seed size distribution about the median. It is calculatedaccording to the following:Span=(D ₈₄ /D ₅₀ +D ₅₀ /D ₁₆)/2

-   -   Where D₅₀ is the median particle size and D₈₄ and D₁₆ are the        particle sizes at the sixteenth and eighty-fourth percentiles on        the cumulative mass percent retained plot, respectively.

In the event that the D₁₆ value falls below the finest sieve size (150um), then the span is calculated according to the following:Span=(D ₈₄ /D ₅₀).

In the event that the D₈₄ value falls above the coarsest sieve size(2360 um), then the span is calculated according to the following:Span=(D ₅₀ /D ₁₆).

In the event that the D₁₆ value falls below the finest sieve size (150um) and the D₈₄ value falls above the coarsest sieve size (2360 um),then the distribution span is taken to be a maximum value of 5.7.

Diameter Test Method

The diameter of a discrete fibrous element or a fibrous element within afibrous structure is determined by using a Scanning Electron Microscope(SEM) or an Optical Microscope and an image analysis software. Amagnification of 200 to 10,000 times is chosen such that the fibrouselements are suitably enlarged for measurement. When using the SEM, thesamples are sputtered with gold or a palladium compound to avoidelectric charging and vibrations of the fibrous element in the electronbeam. A manual procedure for determining the fibrous element diametersis used from the image (on monitor screen) taken with the SEM or theoptical microscope. Using a mouse and a cursor tool, the edge of arandomly selected fibrous element is sought and then measured across itswidth (i.e., perpendicular to fibrous element direction at that point)to the other edge of the fibrous element. A scaled and calibrated imageanalysis tool provides the scaling to get actual reading in μm. Forfibrous elements within a fibrous structure, several fibrous element arerandomly selected across the sample of the fibrous structure using theSEM or the optical microscope. At least two portions of the fibrousstructure are cut and tested in this manner. Altogether at least 100such measurements are made and then all data are recorded forstatistical analysis. The recorded data are used to calculate average(mean) of the fibrous element diameters, standard deviation of thefibrous element diameters, and median of the fibrous element diameters.

Another useful statistic is the calculation of the amount of thepopulation of fibrous elements that is below a certain upper limit. Todetermine this statistic, the software is programmed to count how manyresults of the fibrous element diameters are below an upper limit andthat count (divided by total number of data and multiplied by 100%) isreported in percent as percent below the upper limit, such as percentbelow 1 micrometer diameter or %-submicron, for example. We denote themeasured diameter (in μm) of an individual circular fibrous element asdi.

In the case that the fibrous elements have non-circular cross-sections,the measurement of the fibrous element diameter is determined as and setequal to the hydraulic diameter which is four times the cross-sectionalarea of the fibrous element divided by the perimeter of thecross-section of the fibrous element (outer perimeter in case of hollowfibrous elements). The number-average diameter, alternatively averagediameter is calculated as:

$d_{num} = \frac{\sum\limits_{i = 1}^{n}d_{i}}{n}$Tensile Test Method: Elongation, Tensile Strength, TEA and Modulus

Elongation, Tensile Strength, TEA and Tangent Modulus are measured on aconstant rate of extension tensile tester with computer interface (asuitable instrument is the EJA Vantage from the Thwing-Albert InstrumentCo. Wet Berlin, N.J.) using a load cell for which the forces measuredare within 10% to 90% of the limit of the cell. Both the movable (upper)and stationary (lower) pneumatic jaws are fitted with smooth stainlesssteel faced grips, 25.4 mm in height and wider than the width of thetest specimen. An air pressure of about 60 psi is supplied to the jaws.

Eight usable units of a fibrous structure are divided into two stacks offour samples each. The samples in each stack are consistently orientedwith respect to machine direction (MD) and cross direction (CD). One ofthe stacks is designated for testing in the MD and the other for CD.Using a one inch precision cutter (Thwing Albert JDC-1-10, or similar)cut 4 MD strips from one stack, and 4 CD strips from the other, withdimensions of 1.00 in ±0.01 in wide by 3.0-4.0 in long. Each strip ofone usable unit thick will be treated as a unitary specimen for testing.

Program the tensile tester to perform an extension test, collectingforce and extension data at an acquisition rate of 20 Hz as thecrosshead raises at a rate of 2.00 in/min (5.08 cm/min) until thespecimen breaks. The break sensitivity is set to 80%, i.e., the test isterminated when the measured force drops to 20% of the maximum peakforce, after which the crosshead is returned to its original position.

Set the gauge length to 1.00 inch. Zero the crosshead and load cell.Insert at least 1.0 in of the unitary specimen into the upper grip,aligning it vertically within the upper and lower jaws and close theupper grips. Insert the unitary specimen into the lower grips and close.The unitary specimen should be under enough tension to eliminate anyslack, but less than 5.0 g of force on the load cell. Start the tensiletester and data collection. Repeat testing in like fashion for all fourCD and four MD unitary specimens. Program the software to calculate thefollowing from the constructed force (g) verses extension (in) curve:

Tensile Strength is the maximum peak force (g) divided by the samplewidth (in) and reported as g/in to the nearest 1 g/in.

Adjusted Gauge Length is calculated as the extension measured at 3.0 gof force (in) added to the original gauge length (in).

Elongation is calculated as the extension at maximum peak force (in)divided by the Adjusted Gauge Length (in) multiplied by 100 and reportedas % to the nearest 0.1%

Total Energy (TEA) is calculated as the area under the force curveintegrated from zero extension to the extension at the maximum peakforce (g*in), divided by the product of the adjusted Gauge Length (in)and specimen width (in) and is reported out to the nearest 1 g*in/in².

Replot the force (g) verses extension (in) curve as a force (g) versesstrain curve. Strain is herein defined as the extension (in) divided bythe Adjusted Gauge Length (in). Program the software to calculate thefollowing from the constructed force (g) verses strain curve:

Tangent Modulus is calculated as the slope of the linear line drawnbetween the two data points on the force (g) versus strain curve, whereone of the data points used is the first data point recorded after 28 gforce, and the other data point used is the first data point recordedafter 48 g force. This slope is then divided by the specimen width (2.54cm) and reported to the nearest 1 g/cm.

The Tensile Strength (g/in), Elongation (%), Total Energy (g*in/in²) andTangent Modulus (g/cm) are calculated for the four CD unitary specimensand the four MD unitary specimens. Calculate an average for eachparameter separately for the CD and MD specimens.

Calculations:Geometric Mean Tensile=Square Root of [MD Tensile Strength (g/in)×CDTensile Strength (g/in)]Geometric Mean Peak Elongation=Square Root of [MD Elongation (%)×CDElongation (%)]Geometric Mean TEA=Square Root of [MD TEA (g*in/in²)×CD TEA (g/in²)]Geometric Mean Modulus=Square Root of [MD Modulus (g/cm)×CD Modulus(g/cm)]Total Dry Tensile Strength (TDT)=MD Tensile Strength (g/in)+CD TensileStrength (g/in)Total TEA=MD TEA (g*in/in²)+CD TEA (g*in/in²)Total Modulus=MD Modulus (g/cm)+CD Modulus (g/cm)Tensile Ratio=MD Tensile Strength (g/in)/CD Tensile Strength (g/in)Thickness Method

Thickness of a fibrous structure is measured by cutting 5 samples of afibrous structure sample such that each cut sample is larger in sizethan a load foot loading surface of a VIR Electronic Thickness TesterModel II available from Thwing-Albert Instrument Company, Philadelphia,Pa. Typically, the load foot loading surface has a circular surface areaof about 3.14 in². The sample is confined between a horizontal flatsurface and the load foot loading surface. The load foot loading surfaceapplies a confining pressure to the sample of 15.5 g/cm². The thicknessof each sample is the resulting gap between the flat surface and theload foot loading surface. The thickness is calculated as the averagethickness of the five samples. The result is reported in millimeters(mm).

Shear Viscosity Test Method

The shear viscosity of a filament-forming composition of the presentinvention is measured using a capillary rheometer, Goettfert Rheograph6000, manufactured by Goettfert USA of Rock Hill S.C., USA. Themeasurements are conducted using a capillary die having a diameter D of1.0 mm and a length L of 30 mm (i.e., L/D=30). The die is attached tothe lower end of the rheometer's 20 mm barrel, which is held at a dietest temperature of 75° C. A preheated to die test temperature, 60 gsample of the filament-forming composition is loaded into the barrelsection of the rheometer. Rid the sample of any entrapped air. Push thesample from the barrel through the capillary die at a set of chosenrates 1,000-10,000 seconds⁻¹. An apparent shear viscosity can becalculated with the rheometer's software from the pressure drop thesample experiences as it goes from the barrel through the capillary dieand the flow rate of the sample through the capillary die. The log(apparent shear viscosity) can be plotted against log (shear rate) andthe plot can be fitted by the power law, according to the formulaη=Kγ^(n−1), wherein K is the material's viscosity constant, n is thematerial's thinning index and γ is the shear rate. The reported apparentshear viscosity of the filament-forming composition herein is calculatedfrom an interpolation to a shear rate of 3,000 sec⁻¹ using the power lawrelation.

Weight Average Molecular Weight

The weight average molecular weight (Mw) of a material, such as apolymer, is determined by Gel Permeation Chromatography (GPC) using amixed bed column. A high performance liquid chromatograph (HPLC) havingthe following components: Millenium®, Model 600E pump, system controllerand controller software Version 3.2, Model 717 Plus autosampler andCHM-009246 column heater, all manufactured by Waters Corporation ofMilford, Mass., USA, is utilized. The column is a PL gel 20 μm Mixed Acolumn (gel molecular weight ranges from 1,000 g/mol to 40,000,000g/mol) having a length of 600 mm and an internal diameter of 7.5 mm andthe guard column is a PL gel 20 μm, 50 mm length, 7.5 mm ID. The columntemperature is 55° C. and the injection volume is 200 μL. The detectoris a DAWN® Enhanced Optical System (EOS) including Astra® software,Version 4.73.04 detector software, manufactured by Wyatt Technology ofSanta Barbara, Calif., USA, laser-light scattering detector with K5 celland 690 nm laser. Gain on odd numbered detectors set at 101. Gain oneven numbered detectors set to 20.9. Wyatt Technology's Optilab®differential refractometer set at 50° C. Gain set at 10. The mobilephase is HPLC grade dimethylsulfoxide with 0.1% w/v LiBr and the mobilephase flow rate is 1 mL/min, isocratic. The run time is 30 minutes.

A sample is prepared by dissolving the material in the mobile phase atnominally 3 mg of material/1 mL of mobile phase. The sample is cappedand then stirred for about 5 minutes using a magnetic stirrer. Thesample is then placed in an 85° C. convection oven for 60 minutes. Thesample is then allowed to cool undisturbed to room temperature. Thesample is then filtered through a 5 μm Nylon membrane, type Spartan-25,manufactured by Schleicher & Schuell, of Keene, N.H., USA, into a 5milliliter (mL) autosampler vial using a 5 mL syringe.

For each series of samples measured (3 or more samples of a material), ablank sample of solvent is injected onto the column. Then a check sampleis prepared in a manner similar to that related to the samples describedabove. The check sample comprises 2 mg/mL of pullulan (PolymerLaboratories) having a weight average molecular weight of 47,300 g/mol.The check sample is analyzed prior to analyzing each set of samples.Tests on the blank sample, check sample, and material test samples arerun in duplicate. The final run is a run of the blank sample. The lightscattering detector and differential refractometer is run in accordancewith the “Dawn EOS Light Scattering Instrument Hardware Manual” and“Optilab® DSP Interferometric Refractometer Hardware Manual,” bothmanufactured by Wyatt Technology Corp., of Santa Barbara, Calif., USA,and both incorporated herein by reference.

The weight average molecular weight of the sample is calculated usingthe detector software. A do/dc (differential change of refractive indexwith concentration) value of 0.066 is used. The baselines for laserlight detectors and the refractive index detector are corrected toremove the contributions from the detector dark current and solventscattering. If a laser light detector signal is saturated or showsexcessive noise, it is not used in the calculation of the molecularmass. The regions for the molecular weight characterization are selectedsuch that both the signals for the 90° □ detector for the laser-lightscattering and refractive index are greater than 3 times theirrespective baseline noise levels. Typically the high molecular weightside of the chromatogram is limited by the refractive index signal andthe low molecular weight side is limited by the laser light signal.

The weight average molecular weight can be calculated using a “firstorder Zimm plot” as defined in the detector software. If the weightaverage molecular weight of the sample is greater than 1,000,000 g/mol,both the first and second order Zimm plots are calculated, and theresult with the least error from a regression fit is used to calculatethe molecular mass. The reported weight average molecular weight is theaverage of the two runs of the material test sample.

Fibrous Element Composition Test Method

In order to prepare fibrous elements for fibrous element compositionmeasurement, the fibrous elements must be conditioned by removing anycoating compositions and/or materials present on the external surfacesof the fibrous elements that are removable. An example of a method fordoing so is washing the fibrous elements 3 times with a suitable solventthat will remove the external coating while leaving the fibrous elementsunaltered. The fibrous elements are then air dried at 23° C.±1.0° C.until the fibrous elements comprise less than 10% moisture. A chemicalanalysis of the conditioned fibrous elements is then completed todetermine the compositional make-up of the fibrous elements with respectto the filament-forming materials and the active agents and the level ofthe filament-forming materials and active agents present in the fibrouselements.

The compositional make-up of the fibrous elements with respect to thefilament-forming material and the active agents can also be determinedby completing a cross-section analysis using TOF-SIMs or SEM. Stillanother method for determining compositional make-up of the fibrouselements uses a fluorescent dye as a marker. In addition, as always, amanufacturer of fibrous elements should know the compositions of theirfibrous elements.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

For clarity purposes, the total “% wt” values do not exceed 100% wt.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular examples and/or embodiments of the present inventionhave been illustrated and described, it would be obvious to thoseskilled in the art that various other changes and modifications can bemade without departing from the spirit and scope of the invention. It istherefore intended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A unitary fibrous structure comprising aplurality of water-soluble fibrous elements and a plurality of discretewater-soluble, active agent-containing particles present within theunitary fibrous structure and dispersed throughout the plurality ofwater-soluble fibrous elements, and wherein at least one of thewater-soluble, active agent-containing particles comprises an activeagent selected from one or more surfactants.
 2. The unitary fibrousstructure according to claim 1, wherein at least one of thewater-soluble, active agent-containing particles comprises a medianparticle size of from about 1 μm to about 1600 μm as measured accordingto the Median Particle Size Test Method.
 3. The unitary fibrousstructure according to claim 1, wherein said one or more surfactants areselected from the group consisting of anionic surfactants, cationicsurfactants, nonionic surfactants, zwitterionic surfactants, amphotericsurfactants, and mixtures thereof.
 4. The unitary fibrous structureaccording to claim 3, wherein said one or more surfactants are anionicsurfactants.
 5. The unitary fibrous structure according to claim 3,wherein said one or more surfactants are selected from the groupconsisting of linear or branched alkyl benzene sulfonates, linear orbranched alkoxylated alkyl sulfates, linear or branched alkyl sulfates,and mixtures thereof.
 6. The unitary fibrous structure according toclaim 3, wherein said one or more surfactants are selected from thegroup consisting of linear or branched alkoxylated alkyl sulfates. 7.The unitary fibrous structure of claim 1 wherein at least one of thewater-soluble, active agent-containing particles comprises an activeagent selected from the group consisting of bleaching agents, builders,enzymes, antimicrobials, antibacterials, antifungals, perfumes, perfumedelivery systems, dye transfer inhibiting agents, chelants, brighteners,hueing dyes, suds suppressors, and mixtures thereof.
 8. The unitaryfibrous structure according to claim 1 wherein at least one of thewater-soluble, active agent-containing particles is present as adiscrete particle embedded in the wall of a water-soluble fibrouselement of the fibrous structure.
 9. The unitary fibrous structureaccording to claim 1 wherein the fibrous elements comprise one or morefilaments.
 10. The unitary fibrous structure according to claim 1wherein at least one fibrous element comprises one or morefilament-forming materials.
 11. The unitary fibrous structure accordingto claim 10 wherein the one or more filament-forming materials comprisesa polymer.
 12. The unitary fibrous structure according to claim 11wherein the polymer is selected from the group consisting of: pullulan,hydroxypropylmethyl cellulose, hydroxyethyl cellulose, hydroxypropylcellulose, polyvinyl pyrrolidone, carboxymethyl cellulose, sodiumalginate, xanthan gum, tragacanth gum, guar gum, acacia gum, Arabic gum,polyacrylic acid, methylmethacrylate copolymer, carboxyvinyl polymer,dextrin, pectin, chitin, levan, elsinan, collagen, gelatin, zein,gluten, soy protein, casein, polyvinyl alcohol, carboxylated polyvinylalcohol, sulfonated polyvinyl alcohol, polyethylene glycol, starch,starch derivatives, hemicellulose, hemicellulose derivatives, proteins,chitosan, chitosan derivatives, polyethylene glycol, tetramethyleneether glycol, hydroxymethyl cellulose, and mixtures thereof.
 13. Theunitary fibrous structure according to claim 11 wherein the plurality ofwater-soluble, active agent-containing particles are present in theunitary fibrous structure in two or more layers.
 14. The unitary fibrousstructure according to claim 1 wherein at least one fibrous elementcomprises one or more active agents.
 15. The unitary fibrous structureaccording to claim 14 wherein said one or more active agents comprisesone or more surfactants.
 16. The unitary fibrous structure according toclaim 15 wherein said one or more surfactants are selected from thegroup consisting of anionic surfactants, cationic surfactants, nonionicsurfactants, zwitterionic surfactants, amphoteric surfactants, andmixtures thereof.
 17. The unitary fibrous structure according to claim15 wherein said one or more surfactants are anionic surfactants.
 18. Theunitary fibrous structure according to claim 15 wherein said one or moresurfactants are selected from the group consisting of linear or branchedalkyl benzene sulfonates, linear or branched alkoxylated alkyl sulfates,linear or branched alkyl sulfates, and mixtures thereof.
 19. The unitaryfibrous structure according to claim 15 wherein at least one of thewater-soluble, active agent-containing particles comprises a surfactantthat is different from a surfactant in at least one fibrous element. 20.The unitary fibrous structure according to claim 14 wherein the one ormore active agents is selected from the group consisting of: fabric careactive agents, dishwashing active agents, carpet care active agents,surface care active agents, air care active agents, and mixturesthereof.
 21. The unitary fibrous structure according to claim 14 whereinat least one of the one or more active agents is in the form of aparticle exhibiting a median particle size of 20 μm or less as measuredaccording to the Median Particle Size Test Method.
 22. The unitaryfibrous structure according to claim 21 wherein the particle comprises aperfume microcapsule.
 23. The unitary fibrous structure according toclaim 1 wherein a plurality of the water-soluble, activeagent-containing particles are present in the unitary fibrous structureat a basis weight of from about 1 g/m² to about 5000 g/m².
 24. Theunitary fibrous structure according to claim 23 wherein the fibrouselements are present in the unitary fibrous structure in two or morelayers.
 25. The unitary fibrous structure according to claim 1 whereinthe fibrous elements are present in the unitary fibrous structure at abasis weight of from about 1 g/m² to about 3000 g/m².
 26. The unitaryfibrous structure according to claim 1 wherein at least one of thewater-soluble, active agent-containing particles comprises an enzymeprill, an encapsulated bleaching agent, a perfume microcapsule, or amixture thereof.
 27. The unitary fibrous structure according to claim 1wherein at least one of the fibrous elements exhibits an averagediameter of less than 50 μm as measured according to the Diameter TestMethod.
 28. The unitary fibrous structure according to claim 1 whereinthe unitary fibrous structure exhibits a dissolution time of less than3600 seconds as measured according to the Dissolution Test Method. 29.The unitary fibrous structure according to claim 1 wherein at least oneof the fibrous elements comprises a coating composition present on anexternal surface of the fibrous element.
 30. The unitary fibrousstructure according to claim 1 wherein said unitary fibrous structurecomprises one or more discrete water-insoluble, active agent-containingparticles present within the unitary fibrous structure.
 31. The unitaryfibrous structure according to claim 30 wherein water-insolubleparticles are selected from zeolites, porous zeolites, perfume-loadedzeolites, active loaded zeolites, silicas, perfume-loaded silicas,active loaded silicas, perfume microcapsules, clays and mixturesthereof.
 32. The unitary fibrous structure according to claim 30 whereinat least one of the water-insoluble, active agent-containing particlesis present as a discrete particle between the water-soluble fibrouselements of the fibrous structure.
 33. The unitary fibrous structureaccording to claim 30 wherein at least one of the water-insoluble,active agent-containing particles is present as a discrete particleembedded in the wall of a water-soluble fibrous element of the fibrousstructure.
 34. A multi-ply fibrous structure comprising at least one plyof a unitary fibrous structure according to claim 1 wherein themulti-ply fibrous structure further comprises one or more water-soluble,active agent-containing particles positioned between the at least oneply of unitary fibrous structure and a second ply of a fibrousstructure.
 35. A multi-ply fibrous structure comprising at least one plyof a unitary fibrous structure according to claim
 1. 36. A multi-plyfibrous structure comprising a plurality of plies of a unitary fibrousstructure according to claim
 1. 37. A multi-ply fibrous structurecomprising a plurality of plies of a unitary fibrous structure accordingto claim 1 wherein the external fibrous elements on one of the surfacesof the plies comprises a coating composition.